KR100446200B1 - 2-Cyclohexane-1,3-Dione Benzoyl Derivatives - Google Patents
2-Cyclohexane-1,3-Dione Benzoyl Derivatives Download PDFInfo
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- KR100446200B1 KR100446200B1 KR10-1998-0701569A KR19980701569A KR100446200B1 KR 100446200 B1 KR100446200 B1 KR 100446200B1 KR 19980701569 A KR19980701569 A KR 19980701569A KR 100446200 B1 KR100446200 B1 KR 100446200B1
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- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Abstract
화학식 I의 벤조일 유도체 및 농업적으로 이용가능한 염, 그들의 제조 방법 및 그들의 제초제로서의 용도를 설명한다. The benzoyl derivatives of formula I and agriculturally available salts, their preparation methods and their use as herbicides are described.
<화학식 I><Formula I>
상기 식에서, 치환체 L, M, X, Y 및 n은 제1항에 정의된 의미를 가지며, Wherein the substituents L, M, X, Y and n have the meanings defined in claim 1,
Q는 화학식 II의 시클로헥산-1,3-디온 고리이며, 이 고리는 2-위치에 결합되며;Q is a cyclohexane-1,3-dione ring of Formula II, which is bonded at the 2-position;
<화학식 II><Formula II>
(식 중,(In the meal,
R15, R16, R18 및 R20은 수소 또는 C1-C4-알킬이고;R 15 , R 16 , R 18 and R 20 are hydrogen or C 1 -C 4 -alkyl;
R19는 수소, C1-C4-알킬 또는 -COOR14기이고;R 19 is hydrogen, C 1 -C 4 -alkyl or —COOR 14 group;
R17은 수소, C1-C4-알킬, C3-C4-시클로알킬 (여기서, 이러한 기들은 바람직하다면, 할로겐, C1-C4-알킬티오 또는 C1-C4-알콕시 중에서 1 내지 3 개의 치환체를 가질 수 있음)이거나,R 17 is hydrogen, C 1 -C 4 -alkyl, C 3 -C 4 -cycloalkyl, wherein these groups are preferably 1 in halogen, C 1 -C 4 -alkylthio or C 1 -C 4 -alkoxy To three substituents), or
R17은 테트라히드로피란-3-일, 테트라히드로피란-4-일 또는 테트라히드로티오피란-3-일이거나, 또는R 17 is tetrahydropyran-3-yl, tetrahydropyran-4-yl or tetrahydrothiopyran-3-yl, or
R17과 R20이 함께 결합을 형성하거나 3 내지 6-원의 카르보시클릭 고리를 형성하며,R 17 and R 20 together form a bond or form a 3 to 6 membered carbocyclic ring,
단, Y가 C=O인 경우, X는 NR23이 아니다.However, when Y is C = O, X is not NR 23.
Description
<사용예><Use example>
화학식 I의 벤조일 유도체의 제초 작용을 하기 온실 실험으로 나타낼 수 있었다:The herbicidal action of the benzoyl derivatives of formula I can be shown in the following greenhouse experiments:
사용된 배양 용기는 플라스틱 화분이며, 기질로서 약 3.0 %의 부식토를 첨가한 롬질 (loamy)의 토양을 담고 있었다. 시험 식물의 종자를 각 종별로 분리하여 뿌렸다. The culture vessel used was a plastic pot and contained loamy soils with about 3.0% humus added as substrate. Seeds of the test plants were sprinkled separately for each species.
발아전 처리의 경우, 물 중에 현탁되거나 유화시킨 활성 성분을 잘 분포하도록 하는 노즐을 사용하여 파종 후에 직접 시용하였다. 용기에 물을 넣어 발아 및 성장을 촉진시키고, 식물이 뿌리를 내릴 때까지 투명한 플라스틱 후드로 덮었다. 시험 식물이 활성 성분에 의해서 불리하게 영향을 받지 않는다면, 이러한 커버는 시험 식물이 일정하게 발아하도록 한다. In the case of pre-germination treatment, it was applied directly after sowing by using a nozzle to distribute the active ingredient suspended or emulsified in water well. Water was added to the container to promote germination and growth and covered with a clear plastic hood until the plant took root. If the test plant is not adversely affected by the active ingredient, this cover allows the test plant to germinate constantly.
발아후 처리를 위해서 시험 식물을 먼저 생장 형태에 따라서 3 내지 15 cm의 식물 높이까지 자라게 하고 나서, 물 중에 현탁시키거나 유화된 활성 성분으로 처리하였다. 이를 위해, 시험 식물을 직접 파종하고 동일한 용기 내에서 자라게 하거나, 또는 그들을 우선 묘목으로서 별도로 자라게 하고 난 후, 처리 몇칠 전에 시험 용기 내로 옮겨 심었다. For post-germination treatment the test plants were first grown to a plant height of 3 to 15 cm, depending on the growth morphology, and then treated with suspended or emulsified active ingredients. To this end, the test plants are sown directly and grown in the same container, or they are first grown separately as seedlings, and then transferred into the test container several days before treatment.
발아후 처리에 대한 시용율은 헥타르 당 활성 물질 0.5 내지 0.25 kg이었다.The application rate for post-germination treatment was 0.5 to 0.25 kg of active substance per hectare.
식물은 종에 따라서 10 내지 25 ℃ 또는 20 내지 35 ℃를 유지하였다. 시험 기간을 2 내지 4 주로 연장하였다. 이 시간 동안, 식물들을 키우고 각 처리에 대한 그들의 반응을 평가하였다.The plants were kept at 10-25 ° C. or 20-35 ° C. depending on the species. The trial period was extended from 2 to 4 weeks. During this time, plants were grown and their response to each treatment was evaluated.
평가를 위해서 0 내지 100의 범위를 사용하였다. 100은 식물의 무발아 또는 적어도 기상 부분의 완전히 파괴를 의미하고, 0은 무손상 또는 정상 성장을 의미한하였다. The range of 0-100 was used for evaluation. 100 means no germination or at least complete destruction of the gaseous part of the plant, 0 means intact or normal growth.
온실 실험에서 사용된 식물은 하기 종으로 이루어졌다:The plants used in the greenhouse experiment consisted of the following species:
<표 17>TABLE 17
온실에서 발아후 시용 경우의 제초 활성Herbicidal Activity in Application after Germination in Greenhouse
<표 18>TABLE 18
온실에서 발아후 시용 경우의 제초 활성Herbicidal Activity in Application after Germination in Greenhouse
본 발명은 제초 작용을 갖는 신규의 벤조일 유도체, 벤조일 유도체의 제조 방법, 이를 함유하는 조성물, 및 벤조일 유도체 또는 이러한 유도체를 함유하는 조성물의 잡초를 억제하기 위한 용도에 관한 것이다.The present invention relates to novel benzoyl derivatives having herbicidal action, methods for producing benzoyl derivatives, compositions containing them, and uses for inhibiting weeds of benzoyl derivatives or compositions containing such derivatives.
제초 활성이 있는 2-아로일시클로헥산디온은 예를 들어, 문헌 [EP 283261, EP 90262, EP 135191, EP 186118, EP 186119, EP 186120, EP 319075, WO 9005712, WO 9404524, WO 9408988, JO 3052862 및 JO 3120202]에 기재되어 있다.2-aroylcyclohexanedione with herbicidal activity is described, for example, in EP 283261, EP 90262, EP 135191, EP 186118, EP 186119, EP 186120, EP 319075, WO 9005712, WO 9404524, WO 9408988, JO 3052862 And JO 3120202.
그러나, 공지된 화합물의 제초성 및 농작물에 의한 내성은 단지 제한된 범위에 한해서 만족할 만 한다.However, herbicidal and crop resistance of known compounds are only satisfactory in a limited range.
본 발명의 목적은 개선된 특성을 갖는 신규의 2-아로일시클로헥산디온을 얻는 것이다. It is an object of the present invention to obtain novel 2-aroylcyclohexanediones with improved properties.
본 발명자들은 이러한 목적이 화학식 I의 벤조일 유도체 및 화합물 I의 농업적으로 통상적인 염으로 달성된다는 것을 알아내었다. The inventors have found that this object is achieved with the benzoyl derivatives of formula (I) and the agriculturally common salts of compound (I).
상기 식에서, Where
L 및 M은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시 (여기서, 이러한 기들은 1 내지 5 개의 할로겐 원자 또는 C1-C4-알콕시로 치환될 수 있음), 할로겐, 시아노, 니트로, -(A)m-S(O)nR1기 또는 -(A)m-CO-R2기이고;L and M are hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, wherein these groups are from 1 to 5 halogens Atom or C 1 -C 4 -alkoxy), halogen, cyano, nitro,-(A) m -S (O) n R 1 group or-(A) m -CO-R 2 group ;
Y는 C=O, C=N-R3, CR7-NR5R6, CR7-OR8, CR10R11, CR7-SR8; 수소 또는 C1-C4-알킬로 치환된 1,3-디옥사닐 또는 1,3-디옥솔라닐; 산소, 황 및 질소로부터 선택된 헤테로 원자로 이루어진 기이며;Y is C = O, C = NR 3 , CR 7 -NR 5 R 6 , CR 7 -OR 8 , CR 10 R 11 , CR 7 -SR 8 ; 1,3-dioxanyl or 1,3-dioxolanyl substituted with hydrogen or C 1 -C 4 -alkyl; A group consisting of a hetero atom selected from oxygen, sulfur and nitrogen;
X는 (-CR12R13-), (-CR12R13-CR21R22-), (-CR12=CR13-), (-CR12R13-CR12=CR13-) 또는 NR23이며, X 및 Y 간의 결합은 포화 또는 불포화일 수 있으며;X is (-CR 12 R 13- ), (-CR 12 R 13 -CR 21 R 22- ), (-CR 12 = CR 13- ), (-CR 12 R 13 -CR 12 = CR 13- ) or NR 23 , and the bond between X and Y may be saturated or unsaturated;
A는 O 또는 NR14이고;A is O or NR 14 ;
m은 0 또는 1이고;m is 0 or 1;
n은 0, 1 또는 2이고;n is 0, 1 or 2;
R1은 C1-C4-알킬, C1-C4-할로알킬 또는 NR14이고;R 1 is C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl or NR 14 ;
R2는 C1-C4-알킬, C1-C4-할로알킬, C1-C4-알콕시 또는 NR14이고;R 2 is C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or NR 14 ;
R3은 수소, -NR9R4; C1-C6-알킬, C1-C6-할로알킬, C1-C6-알콕시, C1-C6-할로알콕시, C2-C6-알케닐, C2-C6-할로알케닐, C2-C6-알키닐; 일치환 내지 다치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨); 일- 내지 다치환된 벤질 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨); 일- 내지 다치환된 벤질옥시 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 3 is hydrogen, —NR 9 R 4 ; C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -halo Alkenyl, C 2 -C 6 -alkynyl; Mono- to polysubstituted phenyl wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro); Mono- to polysubstituted benzyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro); Mono- to polysubstituted benzyloxy wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cya O, selected from nitro);
R4는 수소, C1-C6-알킬, C1-C6-할로알킬, C2-C6-알케닐, C2-C6-알키닐, C=O-NR14; 일치환 내지 다치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨); 일- 내지 다치환된 벤질 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 4 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C═O—NR 14 ; Mono- to polysubstituted phenyl wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro); Mono- to polysubstituted benzyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro);
R9는 수소, C1-C6-알킬, C1-C6-할로알킬, C2-C6-알케닐, C2-C6-알키닐, C=O-NR14; 일치환 내지 다치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨); 일- 내지 다치환된 벤질 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 9 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C═O—NR 14 ; Mono- to polysubstituted phenyl wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro); Mono- to polysubstituted benzyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro);
R5 및 R6은 서로 독립적으로, 수소, C1-C6-알킬, C2-C6-알케닐, C1-C4-할로알킬, C2-C6-할로알케닐, C1-C6-알콕시, C1-C6-할로알콕시; 일치환 내지 다치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨); 일- 내지 다치환된 벤질 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 5 and R 6 independently of one another are hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 4 -haloalkyl, C 2 -C 6 -haloalkenyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy; Mono- to polysubstituted phenyl wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro); Mono- to polysubstituted benzyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano , Selected from nitro);
R7은 수소, C1-C6-알킬, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시; 치환되거나 비치환된 페닐 (여기서, 치환체는 1 내지 3 개의 할로겐, C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, 니트로로부터 선택됨)이고; R7과 R21 또는 R7과 R23 또는 R7과 R12는 결합을 형성할 수 있으며;R 7 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy; Substituted or unsubstituted phenyl, wherein the substituent is selected from 1 to 3 halogens, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, nitro; R 7 and R 21 or R 7 and R 23 or R 7 and R 12 may form a bond;
R8은 수소, C1-C6-알킬, C1-C4-할로알킬, 치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨); 치환된 벤질 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 8 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, substituted phenyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, nitro); Substituted benzyl, wherein the substituent is selected from C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, nitro )ego;
R10 및 R11은 서로 독립적으로, 수소, C1-C6-알킬; 비치환 또는 치환된 페닐 (여기서, 치환체는 1 내지 3 개의 할로겐, C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, 니트로로부터 선택됨)이고; R10과 R12 또는 R10과 R23 또는 R10과 R21은 결합을 형성할 수 있으며;R 10 and R 11 are, independently from each other, hydrogen, C 1 -C 6 -alkyl; Unsubstituted or substituted phenyl, wherein the substituent is selected from 1 to 3 halogens, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, nitro; R 10 and R 12 or R 10 and R 23 or R 10 and R 21 may form a bond;
R12 및 R13은 서로 독립적으로, 수소, C1-C6-알킬, C1-C6-할로알킬, C1-C6-알콕시, C1-C6-할로알콕시; 비치환되거나 치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 12 and R 13 are, independently from each other, hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy; Unsubstituted or substituted phenyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, Selected from nitro);
R14는 C1-C4-알킬이고;R 14 is C 1 -C 4 -alkyl;
R21은 수소, C1-C6-알킬, C1-C6-할로알킬, C1-C6-알콕시, C1-C6-할로알콕시; 비치환되거나 치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 21 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy; Unsubstituted or substituted phenyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, Selected from nitro);
R22는 수소, C1-C6-알킬, C1-C6-할로알킬, C1-C6-알콕시, C1-C6-할로알콕시; 비치환되거나 치환된 페닐 (여기서, 치환체는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로부터 선택됨)이고;R 22 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy; Unsubstituted or substituted phenyl, wherein the substituents are C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, Selected from nitro);
R23은 수소, C1-C6-알킬, C2-C6-알케닐, C1-C6-알콕시, 페닐 또는 벤질 (이는 C1-C4-알킬, C1-C4-알콕시, C1-C4-할로알콕시, C1-C4-할로알킬, 할로겐, 시아노, 니트로로 치환될 수 있음)이고;R 23 is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy, phenyl or benzyl (which is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy , C 1 -C 4 - haloalkoxy, C 1 -C 4 - haloalkyl, halogen, cyano, can be substituted with a nitro group) and;
Q는 화학식 II의 시클로헥산-1,3-디온 고리이며, 이 고리는 2-위치에서 결합되며; Q is a cyclohexane-1,3-dione ring of formula II, which is bonded at the 2-position;
(식 중,(In the meal,
R15, R16, R18 및 R20은 수소 또는 C1-C4-알킬이고;R 15 , R 16 , R 18 and R 20 are hydrogen or C 1 -C 4 -alkyl;
R19는 수소, C1-C4-알킬 또는 -COOR14기이고;R 19 is hydrogen, C 1 -C 4 -alkyl or —COOR 14 group;
R17은 수소, C1-C4-알킬, C3-C4-시클로알킬 (여기서, 이러한 기들은 할로겐, C1-C4-알킬티오 또는 C1-C4-알콕시 중에서 선택된 1 내지 3 개의 치환체로 치환될 수 있음)이거나,R 17 is hydrogen, C 1 -C 4 -alkyl, C 3 -C 4 -cycloalkyl, wherein these groups are 1 to 3 selected from halogen, C 1 -C 4 -alkylthio or C 1 -C 4 -alkoxy May be substituted with 4 substituents)
R17은 테트라히드로피란-3-일, 테트라히드로피란-4-일 또는 테트라히드로티오피란-3-일이거나, 또는R 17 is tetrahydropyran-3-yl, tetrahydropyran-4-yl or tetrahydrothiopyran-3-yl, or
R17과 R20이 함께 결합을 형성하거나 3 내지 6-원의 카르보시클릭 고리를 형성함)R 17 and R 20 together form a bond or form a 3 to 6 membered carbocyclic ring)
단, Y가 C=O인 경우, X는 NR23이 아니다.However, when Y is C = O, X is not NR 23.
화학식 Ia 내지 Ie의 화합물은 화학식 II의 화합물을 화학식 III의 벤조산 유도체와 반응시키고 재배열시킴으로써 얻어진다.Compounds of Formulas Ia through Ie are obtained by reacting and rearranging a compound of Formula II with a benzoic acid derivative of Formula III.
<반응식 1><Scheme 1>
상기 반응식에서, T는 할로겐 또는 OH를 의미하며, L, M, X, Y 및 n은 상기에 정의한 의미를 갖는다.In the above scheme, T means halogen or OH, and L, M, X, Y and n have the meanings defined above.
반응 순서의 제1 단계인 아실화는 통상적으로 공지된 방법, 예를 들어, 화학식 III (T=Cl)의 산 클로라이드 또는 화학식 III (T=OH)의 활성화된 카르복실산을 예를 들어, DCC (디시클로카르보디이미드) 또는 문헌에 공지된 유사한 작용제, 예를 들어, 트리페닐포스핀/DEAD = 디에틸 아조디카르복실레이트, 2-피리딘 디술피드/트리페닐포스핀과 함께, 적합하다면 보조 염기의 존재하에, 시클로헥산디온(화학식 II)의 용액 또는 현탁액에 가함으로써 수행된다. 이 경우, 반응물 및 보조 염기는 편의상 동몰량으로 사용된다. 예를 들어, 화합물 II을 기준으로 1.2 내지 1.5 몰량의 약간 과량의 보조 염기가 특정 상태하에서 유리할 수 있다. Acylation, which is the first step in the reaction sequence, is commonly carried out by known methods, for example acid chlorides of formula III (T = Cl) or activated carboxylic acids of formula III (T = OH), for example DCC (Dicyclocarbodiimide) or similar agents known in the literature, such as triphenylphosphine / DEAD = diethyl azodicarboxylate, 2-pyridine disulfide / triphenylphosphine, if appropriate, auxiliaries In the presence of a base, it is carried out by addition to a solution or suspension of cyclohexanedione (Formula II). In this case, the reactants and the auxiliary base are used in equimolar amounts for convenience. For example, 1.2 to 1.5 molar amount of slightly excess auxiliary base based on compound II may be advantageous under certain conditions.
적합한 보조 염기는 3급 알킬아민, 피리딘 또는 알칼리 금속 탄산염이다. 사용되는 용매는 예를 들어, 염화메틸렌, 디옥산, 디에틸 에테르, 톨루엔, 아세토니트릴 또는 에틸 아세테이트일 수 있다.Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. The solvent used may be, for example, methylene chloride, dioxane, diethyl ether, toluene, acetonitrile or ethyl acetate.
산 클로라이드를 첨가하는 동안, 반응 혼합물은 바람직하게는 0 내지 10 ℃로 냉각시키고, 이어서 반응이 종결될 때까지 20 내지 100 ℃, 특히 25 내지 50 ℃에서 교반시킨다. 마무리 처리는 통상적인 방법, 예를 들어, 반응 혼합물을 물에 붓고, 유용한 생성물을 예를 들어, 염화 메틸렌으로 추출함으로써 수행된다. 유기상을 건조시키고 용매를 제거한 후, 추가의 정제없이 조질의 에놀 에스테르를 재배열시킬 수 있다. 시클로헥산-1,3-디온의 벤조일 에놀 에스테르에 대한 제조예가 예를 들어, 문헌[EP-A 186118 또는 US 4,780,127]에 기재되어 있다.During the addition of the acid chloride, the reaction mixture is preferably cooled to 0 to 10 ° C and then stirred at 20 to 100 ° C, in particular 25 to 50 ° C, until the reaction is complete. The finishing treatment is carried out by conventional methods, for example by pouring the reaction mixture into water and extracting the useful product, for example with methylene chloride. After drying the organic phase and removing the solvent, the crude enol ester can be rearranged without further purification. Examples of preparations for the benzoyl enol esters of cyclohexane-1,3-dione are described, for example, in EP-A 186118 or US 4,780,127.
화학식 Ia 내지 Ie의 화합물로의 에놀 에스테르의 재배열은 편의상 20 내지 40 ℃의 용매 중에서, 또는 보조 염기의 존재 및 촉매로서 시아노 화합물의 보조하에 수행된다.Rearrangement of the enol esters to the compounds of formulas (la)-(e) is conveniently carried out in a solvent at 20-40 ° C., or in the presence of an auxiliary base and with the aid of a cyano compound as catalyst.
사용되는 용매는 예를 들어, 아세토니트릴, 염화메틸렌, 1,2-디클로로에탄, 에틸 아세테이트 또는 톨루엔일 수 있다. 바람직한 용매는 아세토니트릴이다. 적합한 보조 염기는 3급 알킬아민, 피리딘 또는 알칼리 금속 탄산염이고, 바람직하게는 벤조일 에놀 에스테르를 기준으로 동몰량 또는 4 배의 과량으로 사용된다. 바람직한 보조 염기는 2 배량의 트리에틸아민이다. The solvent used may be, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl acetate or toluene. Preferred solvent is acetonitrile. Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates, preferably used in equimolar amounts or in excess of 4 times based on the benzoyl enol ester. Preferred auxiliary bases are two times triethylamine.
적합한 촉매는 시안화칼륨, 아세톤 시아노히드린 및 트리메틸실릴 시아나이드이며, 바람직하게는 에놀 에스테르를 기준으로 1 내지 50 몰%의 양으로 사용된다. 바람직하게는, 아세톤 시아노히드린이 예를 들어, 5 내지 15 몰%, 특히 10 몰%의 양으로 첨가된다. 시아나이드-촉매된, 에놀 에스테르의 재배열의 실시예가 예를 들어, 문헌[EP-A 186118 또는 US 4,780,127]에 기재되어 있다. Suitable catalysts are potassium cyanide, acetone cyanohydrin and trimethylsilyl cyanide, preferably used in amounts of 1 to 50 mole percent, based on the enol ester. Preferably, acetone cyanohydrin is added in an amount of, for example, 5 to 15 mol%, in particular 10 mol%. Examples of rearrangements of cyanide-catalyzed, enol esters are described, for example, in EP-A 186118 or US 4,780,127.
마무리 처리는 통상적인 방법, 예를 들어, 반응 혼합물을 5 % 농도의 염산 또는 황산과 같은 희석 무기산으로 산성화시키고, 염화메틸렌 또는 에틸 아세테이트와 같은 유기 용매로 추출함으로써 수행된다. 정제를 위하여, 추출물을 냉각된 5 내지 10 % 농도의 알칼리 금속 탄산염 용액으로 추출하고, 최종 생성물을 수성상으로 통과시킨다. 수용액을 산성화함으로써, 화학식 Ia 내지 Ie의 생성물을 염화메틸렌 또는 에틸 아세테이트로 침전시키거나 다시 추출하고 건조시킨 후, 용매를 제거한다. Finishing is carried out by conventional methods, for example by acidifying the reaction mixture with a dilute inorganic acid such as hydrochloric acid or sulfuric acid at a concentration of 5% and extracting with an organic solvent such as methylene chloride or ethyl acetate. For purification, the extract is extracted with a cooled 5-10% concentration of alkali metal carbonate solution and the final product is passed through an aqueous phase. By acidifying the aqueous solution, the products of formulas (la)-(e) are precipitated with methylene chloride or ethyl acetate or extracted again and dried before the solvent is removed.
출발 물질로서 사용되는 화학식 II의 1,3-디케톤은 공지된 화합물이며, 자체 공지된 방법으로 제조될 수 있으며, 예를 들어, 문헌[EP-A 71707, EP-A 142741, EP-A 243313, US 4,249,937 및 WO 92/13821]에 기재되어 있다. 시클로헥산디온 및 디메돈은 시판되고 있는 화합물이다. 1,3-diketones of formula (II) used as starting materials are known compounds and can be prepared by methods known per se, for example, EP-A 71707, EP-A 142741, EP-A 243313. , US 4,249,937 and WO 92/13821. Cyclohexanedione and dimedone are commercially available compounds.
화학식 III의 벤조산은 다음과 같이 제조될 수 있다:Benzoic acid of formula III can be prepared as follows:
예를 들어, 화학식 III (T = Cl)의 벤조일 클로라이드과 같은 벤조일 할라이드는 공지된 방법, 즉 화학식 III (T = OH)의 벤조산을 티오닐 클로라이드와 반응시킴으로써 제조된다. 화학식 III (T = OH)의 벤조산은 화학식 III (T = C1-C4-알콕시)의 상응하는 에스테르의 산 가수분해 또는 염기 가수분해에 의한 공지된 방법으로 제조할 수 있다.For example, benzoyl halides such as benzoyl chloride of formula III (T = Cl) are prepared by known methods, ie by reacting benzoic acid of formula III (T = OH) with thionyl chloride. Benzoic acids of formula III (T = OH) can be prepared by known methods by acid or base hydrolysis of the corresponding esters of formula III (T = C 1 -C 4 -alkoxy).
화학식 III의 중간체는 몇몇 경우에 공지되어 있거나, 문헌에 공지된 방법으로 제조할 수 있다.Intermediates of formula III are known in some cases or may be prepared by methods known in the literature.
<반응식 2><Scheme 2>
이 후, 예를 들어, 반응식 2에 나타내어진 알킬티오 화합물 IV은 문헌 [J. Med. Chem. 1984, 27, 1516]에 기술된 것과 같은 치환된 할로알케닐, 문헌 [J. Org. Chem. 1980, 45, 4611 또는 J. Am. Chem. Soc. 1983, 105, 883]에 기술된 것과 같은 치환된 알키닐카르복실산, 문헌 [Chem. Ber. 1925, 58, 1612]에 기술된 것과 같은 치환된 할로알킬카르복실산과 알칼리 금속 수산화물, 알칼리 금속 수화물 또는 알칼리 금속 탄산염과 같은 염기의 존재하에 반응시킬 수 있다. 생성되는 화합물 V를 프리이델-크라프트 (Friedel-Crafts) 조건하에 루이스산 또는 양성자성 산의 첨가로 고리화시킨다. 문헌[Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1612; Chem. Ber. 1926, 59, 1072; Phosp. 및 Sulf. 1984, 19, 31]에 기재된 대로, 바람직한 루이스산은 AlCl3 또는 SnCl4이고, 바람직한 양성자성 산은 다중인산 및 황산이다.Thereafter, for example, the alkylthio compound IV shown in Scheme 2 is described in J. Med. Chem. Substituted haloalkenyl, such as described in 1984, 27, 1516, J. Org. Chem. 1980, 45, 4611 or J. Am. Chem. Soc. 1983, 105, 883, substituted alkynylcarboxylic acids, such as described in Chem. Ber. Substituted haloalkylcarboxylic acids such as those described in 1925, 58, 1612 can be reacted in the presence of a base such as an alkali metal hydroxide, an alkali metal hydrate or an alkali metal carbonate. The resulting compound V is cyclized by the addition of Lewis or protic acid under Friedel-Crafts conditions. Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1612; Chem. Ber. 1926, 59, 1072; Phosp. And Sulf. 1984, 19, 31, preferred Lewis acids are AlCl 3 or SnCl 4 , and preferred protic acids are polyphosphoric acid and sulfuric acid.
티오크로메논산은 예를 들어, 문헌[Ann. Chem. 1964, 680, 40]에 기재한 대로, 치환된 티오페놀산을 오산화인 존재하에 치환된 α-알킬아세트산 에스테르와 반응시키거나, 예를 들어, 3-할로티오크로마논산으로부터 할로겐화수소를 제거함으로써 추가로 제조할 수 있다.Thiochromenoic acid is described, for example, in Ann. Chem. 1964, 680, 40, further by reacting a substituted thiophenolic acid with a substituted α-alkylacetic acid ester in the presence of phosphorus pentoxide, or by removing hydrogen halide from, for example, 3-halothiochromanoic acid. It can be prepared as.
알킬티오 화합물 IV를 예를 들어, 상응하는 아닐린으로부터 샌드메이어 (Sandmeyer) 반응에 의해서 얻을 수 있으며, 문헌[Organicum 19th Edition 1992, 552 ff]에 기재된 대로, 그들의 일부는 적당한 니트로 화합물의 환원에 의해서 합성된다. Alkylthio compounds IV can be obtained, for example, from the corresponding aniline by Sandmeyer reactions, some of which are synthesized by reduction of the appropriate nitro compound, as described in Organanicum 19th Edition 1992, 552 ff. do.
예를 들어, X가 (-CR12R13-)이거나 (-CR12R13CR21R22-)이고, Y가 C=O, T가 C1-C4-알콕시인 경우, 반응식 2에 기재된 티오크로모논 에스테르 또는 디히드로벤조티오펜 에스테르는 용매 또는 물 중에서 상기 언급한 염기 중 하나의 존재하에 알킬티오 화합물 IV를 할로프로피온산 또는 할로아세트산으로 알킬화시켜 제조되고 화합물 VI로 고리화시킬 수 있다.For example, if X is (-CR 12 R 13- ) or (-CR 12 R 13 CR 21 R 22- ), Y is C = O and T is C 1 -C 4 -alkoxy, The thiochromemonone esters or dihydrobenzothiophene esters described can be prepared by alkylation of alkylthio compound IV with halopropionic acid or haloacetic acid in the presence of one of the bases mentioned above in solvent or water and cyclized to compound VI. .
이 경우, 반응물 및 염기는 편의상 동몰량으로 사용된다. 반응 혼합물을 바람직하게는 20 내지 100 ℃, 특히 20 내지 40 ℃에서 교반시킨다. 마무리 처리는 예를 들어, 반응 혼합물을 물에 붓고, 염산 또는 황산과 같은 무기산을 사용하여 수성상이 산성이 되도록 하고, 유용한 생성물을 흡입으로 여과시키거나 염화메틸렌 또는 에틸 아세테이트로 추출한 후, 그 추출물을 건조시키고 용매를 제거하는 그러한 방법으로 수행된다. 에스테르는 추가 정제없이 반응시킬 수 있다.In this case, the reactants and the base are used in equimolar amounts for convenience. The reaction mixture is preferably stirred at 20 to 100 ° C, in particular at 20 to 40 ° C. The finishing treatment can, for example, pour the reaction mixture into water, make the aqueous phase acidic with an inorganic acid such as hydrochloric acid or sulfuric acid, filter the useful product by suction or extract with methylene chloride or ethyl acetate, and then extract the extract. Is carried out in such a way as to dry and remove the solvent. The ester can be reacted without further purification.
예를 들어, 40 내지 140 ℃, 특히 70 내지 100 ℃의 다중인산 중에서 화합물 V를 교반시킴으로써, 또는 산 클로라이드로의 전환을 통해 카르복실산을 활성화시키고, 용매 중에 AlCl3 또는 SnCl4와 같은 루이스산을 2 내지 6, 특히 3.5 내지 4.5 몰당량으로 가하여 교반시키거나 또는 황산 중에서 교반시킴으로써, 화학식 III의 중간체를 자체 공지된 방식으로, 즉, 얼음물을 가하고 흡입으로 유용한 생성물을 여과하거나 에틸 아세테이트 또는 염화메틸렌으로 수성상을 추출, 건조시키고 용매를 제거하는 방식으로 마무리 처리함으로써 얻어진다.For example, carboxylic acids are activated by stirring compound V in polyphosphoric acid at 40-140 ° C., in particular 70-100 ° C., or via conversion to acid chloride, and Lewis acids such as AlCl 3 or SnCl 4 in the solvent. By adding 2 to 6, in particular 3.5 to 4.5 molar equivalents, or stirring in sulfuric acid, the intermediate of formula III is filtered in a known manner, ie by adding ice water and inhaling the useful product by inhalation or by ethyl acetate or methylene chloride It is obtained by finishing the process in such a manner that the aqueous phase is extracted, dried and the solvent is removed.
예를 들어, X가 에틸렌기 (-CR12=CR13-)이고, Y가 C=O, T가 C1-C4-알콕시인 경우, 티오크로메논 에스테르는 예를 들어, 아릴티오 화합물을 0 내지 140 ℃의 물 또는 용매 중에서 아세틸렌카르복실산 유도체와 반응시킴으로써 전환될 수 있다. 마무리 처리는 자체 공지된 방식, 예를 들어, 물 및 염산과 같은 희석 무기산을 가함으로써 수행될 수 있다. 유용한 생성물을 흡입으로 여과시키고, 염화메틸렌 또는 에틸 아세테이트로 추출한 후, 건조시키고 용매를 제거함으로써 얻어진다.For example, when X is an ethylene group (-CR 12 = CR 13- ), Y is C═O and T is C 1 -C 4 -alkoxy, the thiochromenone ester may be, for example, an arylthio compound. It can be converted by reacting with an acetylenecarboxylic acid derivative in water or solvent at 0 to 140 ° C. The finishing treatment can be carried out in a manner known per se, for example by adding dilute inorganic acids such as water and hydrochloric acid. The useful product is obtained by filtration by suction, extraction with methylene chloride or ethyl acetate, followed by drying and removal of the solvent.
화학식 III의 중간체는 문헌에 공지된 반응, 예를 들어, 문헌[Jerry March, Advanced Organic Chemistry, Fourth Ed., eg. p. 910ff]에 기재된 환원 반응, 문헌[Jerry March, Advanced Organic Chemistry, Fourth Ed., eg. 934, 935, 1039, 1226, 405ff]에 기재된 옥심화, 문헌[Jerry March, Advanced Organic Chemistry, Fourth Ed.]에 기재된 이민 및 아민으로의 전환, 문헌[Jerry March, Advanced Organic Chemistry, Fourth Ed.]에 기재된 케탈화, 알킬화, 할로겐화, 제거 반응, 산화 반응에 의해서 추가 기능화시킬 수 있다. Intermediates of formula (III) can be prepared by reactions known in the literature, for example in Jerry March, Advanced Organic Chemistry, Fourth Ed., Eg. p. 910ff, the reduction reaction described in Jerry March, Advanced Organic Chemistry, Fourth Ed., Eg. 934, 935, 1039, 1226, 405ff, conversion to imines and amines as described in Jerry March, Advanced Organic Chemistry, Fourth Ed., Jerry March, Advanced Organic Chemistry, Fourth Ed. Further functionalization may be achieved by ketalization, alkylation, halogenation, removal reactions, or oxidation reactions described in.
3-알콕시-1,2-벤즈이소티아졸-1,1-디옥시드의 산 또는 3-알콕시-1,2-벤즈이소티아졸의 산은 상응하는 사카린 유도체 또는 1,2-벤즈이소티아졸로부터 출발하여, 적합하다면, 트리에틸아민과 같은 보조 염기의 존재하에 PCl5, POCl3 또는 염소 및 알코올과 반응시킴으로써 얻어질 수 있으며, 이는 예를 들어, US 4,571,429, 문헌 [Arch. Pharm. 1984, 317, 807], US 4,461,901, US 450,916, 문헌[J. Med. Chem. 1986, 29, 359]에 기재되어 있다. 사카린카르복실산은 문헌[Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, German Offenlegungsschrift 3607343, German Patant Application P44 27 995,7]에 공지된 방법으로 얻을 수 있다.The acid of 3-alkoxy-1,2-benzisothiazole-1,1-dioxide or the acid of 3-alkoxy-1,2-benzisothiazole is derived from the corresponding saccharin derivative or 1,2-benzisothiazole. Starting, if appropriate, it can be obtained by reacting with PCl 5 , POCl 3 or chlorine and an alcohol in the presence of an auxiliary base such as triethylamine, see for example US Pat. No. 4,571,429, Arch. Pharm. 1984, 317, 807, US 4,461,901, US 450,916, J. Med. Chem. 1986, 29, 359. Saccharincarboxylic acid is described in Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, German Offenlegungsschrift 3607343, German Patant Application P44 27 995,7.
벤조-1,4-옥사티인산 유도체는 몇몇 경우, 예를 들어, 문헌[J. Org. Chem, 1968, 33, 456]에 공지되어 있거나, 예를 들어, 문헌[Chem. Comm. 1975, 451, J. Org. Chem, 1974, 39, 1881, J. Am. Chem. Soc. 1954, 76, 1068]에 기재된 대로, 상응하는 페놀 유도체로부터의 반응에 의해서, 또는 예를 들어, 문헌[J. Het. Chem. 1983, 20, 867]에 기재된 바와 같은 할로겐-치환된 티오페놀 유도체의 치환 반응 및 산화, 환원 또는 첨가 반응과 같은 제2차 반응의 결합에 의해서 합성될 수 있다. Benzo-1,4-oxaphosphate derivatives are, in some cases, described, for example, in J. Pat. Org. Chem, 1968, 33, 456 or are described, for example, in Chem. Comm. 1975, 451, J. Org. Chem, 1974, 39, 1881, J. Am. Chem. Soc. 1954, 76, 1068, by reaction from the corresponding phenol derivatives, or for example in J. Chem. Het. Chem. 1983, 20, 867 can be synthesized by combining a reaction of the halogen-substituted thiophenol derivatives and secondary reactions such as oxidation, reduction or addition.
또한, 화학식 III의 벤조산은 상응하는 화학식 VII의 브로모- 또는 요오드-치환된 화합물을 승온에서 팔라듐, 니켈, 코발트 또는 로듐 전이 금속 촉매 및 염기 존재하에 일산화탄소 및 물과 반응시킴으로써 얻을 수 있다. The benzoic acid of formula III can also be obtained by reacting the corresponding bromo- or iodine-substituted compound of formula VII with carbon monoxide and water in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and base at elevated temperatures.
<반응식 3><Scheme 3>
T는 OH, C1-C4-알콕시이며,T is OH, C 1 -C 4 -alkoxy,
Y, L, M 및 X는 상기에 정의한 의미를 갖는다.Y, L, M and X have the meanings defined above.
촉매인 니켈, 코발트, 로듐 및 특히, 팔라듐은 금속 형태 또는 통상적인 염의 형태, 예를 들어, PdCl2, RhCl3·H2O와 같은 할로겐 화합물, Pd(OAc)2와 같은 아세테이트, 시아나이드 등의 형태의 공지된 원자가 상태로 존재할 수 있다. 3급 포스핀과의 금속 착체, 금속 알킬카르보닐, CO2(CO)8, Ni(CO)4와 같은 금속 카르보닐, (PPh3)2Ni(CO)2와 같은 3급 포스핀과의 금속 카르보닐 착체 또는 3급 포스핀과 결합된 전이 금속염이 추가로 존재할 수 있다. 촉매가 팔라듐인 경우에 마지막에 언급한 예가 특히 바람직하다. 포스핀 리간드의 성질은 매우 변하기 쉽다. 예를 들어, 그들을 하기 화학식으로 나타낼 수 있다:The catalysts nickel, cobalt, rhodium and in particular palladium are in metal form or in the form of conventional salts, for example halogen compounds such as PdCl 2 , RhCl 3 .H 2 O, acetates such as Pd (OAc) 2 , cyanide and the like. It may exist in a known valence state in the form of. Metal complexes with tertiary phosphines, metal alkylcarbonyls, metal carbonyls such as CO 2 (CO) 8 , Ni (CO) 4 , tertiary phosphines such as (PPh 3 ) 2 Ni (CO) 2 There may further be transition metal salts associated with metal carbonyl complexes or tertiary phosphines. Particular preference is given to the last mentioned example when the catalyst is palladium. The nature of phosphine ligands is very variable. For example, they can be represented by the formula:
상기 식에서 In the above formula
n은 1, 2, 3 또는 4이고, R24 내지 R27라디칼은 C1-C6-알킬과 같은 저분자량 알킬, 아릴, C1-C4-알킬아릴, 예를 들어, 벤질, 페네틸 또는 아릴옥시이다. 아릴은 예를 들어, 나프틸, 안트릴 및 바람직하게는 비치환되거나 치환된 페닐, 이 때, 치환체에 대해서는 카르복실화 반응에 대해 그들이 불활성이어야 하며, 달리 그들은 매우 다양하여 모든 불활성 C-유기 라디칼, 예를 들어, 메틸과 같은 C1-C6-알킬 라디칼, COOH, COOM (여기서, M은 예를 들어, 알칼리 금속, 알칼리 토금속 또는 알루미늄염임)와 같은 카르복실 라디칼, 또는 C1-C6-알콕시 라디칼과 같이 산소를 통해 결합된 C-유기 라디칼을 포함한다.n is 1, 2, 3 or 4, and R 24 to R 27 radicals are low molecular weight alkyl, such as C 1 -C 6 -alkyl, aryl, C 1 -C 4 -alkylaryl, for example benzyl, phenethyl Or aryloxy. Aryl is, for example, naphthyl, anthryl and preferably unsubstituted or substituted phenyl, in which case they should be inert to the carboxylation reaction for the substituents, otherwise they vary so widely that all inert C-organic radicals For example, a C 1 -C 6 -alkyl radical such as methyl, COOH, COOM (where M is, for example, an alkali metal, alkaline earth metal or aluminum salt), or C 1 -C 6 C-organic radicals bonded through oxygen, such as -alkoxy radicals.
포스핀 착체는 자체 공지된 방식, 예를 들어, 본 명세서 개시부에 언급한 문헌에 기재된 것과 같이 제조될 수 있다. 예를 들어, 사용되는 출발 물질은 PdCl2 또는 Pd(OCOCH3)2와 같은 통상적으로 시판되고 있는 금속염이며, 예를 들어, P(C6H5)3, P(n-C4H9)3, PCH3(C6H5)3, 1,2-비스(디페닐포스피노)에탄과 같은 포스핀도 있다.The phosphine complexes can be prepared in a manner known per se, for example as described in the literature mentioned at the beginning of this specification. For example, starting materials used are commercially available metal salts such as PdCl 2 or Pd (OCOCH 3 ) 2 , for example P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , There are also phosphines such as PCH 3 (C 6 H 5 ) 3 , 1,2-bis (diphenylphosphino) ethane.
포스핀의 양은 전이 금속을 기준으로 하여 통상 0 내지 20 몰당량, 특히 0.1 내지 10 몰당량, 특히 바람직하게는 1 내지 5 몰당량이다. The amount of phosphine is usually from 0 to 20 molar equivalents, in particular from 0.1 to 10 molar equivalents, particularly preferably from 1 to 5 molar equivalents, based on the transition metal.
전이 금속의 양은 중요하지 않다. 물론, 비용의 문제로 인하여, 오히려 소량, 예를 들어, 출발 물질 II 또는 III을 기준으로 0.1 내지 10 몰%, 특히 1 내지 5 몰%가 사용된다. The amount of transition metal is not critical. Of course, due to cost concerns, rather small amounts, for example 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting materials II or III are used.
벤조산 III (T = OH)의 제조를 위한 반응은 출발 물질 VI을 기준으로 일산화탄소 및 최소한의 몰당량의 물을 가하여 수행된다. 반응 성분인 물을 또한 용매로서 동시에 사용할 수 있고, 최대량은 중요하지 않다.The reaction for the preparation of benzoic acid III (T = OH) is carried out by adding carbon monoxide and a minimum molar equivalent of water based on the starting material VI. Water, which is a reaction component, can also be used simultaneously as a solvent, and the maximum amount is not critical.
그러나, 사용되는 출발 물질 및 촉매에 따라서, 반응 성분을 대신하여 용매로서 또다른 불활성 용매 또는 카르복실화에 사용되는 염기를 사용하는 것도 유리할 수 있다. However, depending on the starting materials and catalysts used, it may also be advantageous to use another inert solvent or base used for carboxylation as a solvent in place of the reaction components.
적당한 불활성 용매는 카르복실화 반응에서 통상적인 용매, 예를 들어, 톨루엔, 크실렌, 헥산, 펜탄, 시클로펜탄과 같은 탄화수소, 예를 들어, 메틸 tert-부틸 에테르와 같은 에테르, 테트라히드로푸란, 디옥산, 디메톡시에탄, 디메틸포름아미드와 같은 치환된 아미드, 테트라-C1-C4-알킬-우레아와 같은 과치환된 우레아, 또는 벤조니트릴 또는 아세토니트릴과 같은 니트릴이다.Suitable inert solvents are conventional solvents in the carboxylation reaction, for example hydrocarbons such as toluene, xylene, hexane, pentane, cyclopentane, for example ethers such as methyl tert-butyl ether, tetrahydrofuran, dioxane , Substituted amides such as dimethoxyethane, dimethylformamide, oversubstituted ureas such as tetra-C 1 -C 4 -alkyl-urea, or nitriles such as benzonitrile or acetonitrile.
방법의 바람직한 실시태양에서, 반응 성분들 중 하나, 특히 염기는 부가 용매가 필요하지 않도록 과량으로 사용된다. In a preferred embodiment of the process, one of the reaction components, in particular the base, is used in excess so that no additional solvent is required.
공정에 적합한 염기는 반응 중에 생성된 요오드화수소 또는 브롬화수소와 결합할 수 있는 모든 불활성 염기이다. 본 명세서에서 언급될 수 있는 예는 tert-알킬아민과 같은 3급 아민, 트리에틸아민과 같은 트리알킬아민, N-메틸피페리딘 또는 N,N'-디메틸피페라진과 같은 시클릭 아민, 피리딘, 알칼리 금속 탄산염 또는 탄산수소, 또는 테트라-C1-C4-알킬우레아와 같은 테트라알킬-치환된 우레아 유도체, 예를 들어 테트라메틸우레아이다.Suitable bases for the process are all inert bases capable of binding to the hydrogen iodide or hydrogen bromide produced during the reaction. Examples that may be mentioned herein include tertiary amines such as tert-alkylamines, trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N'-dimethylpiperazine, pyridine , Alkali metal carbonates or hydrogen carbonates, or tetraalkyl-substituted urea derivatives such as tetra-C 1 -C 4 -alkylurea, for example tetramethylurea.
염기의 양은 중요하지 않으며, 통상 1 내지 10 몰, 특히 1 내지 5 몰이 사용된다. 염기가 용매로서 동시에 사용되는 경우, 그 양은 일반적으로 반응 성분들을 용해시키는데 비례하며, 실용적 이유 및 비용을 절감하고 작은 반응 용기를 사용하여 반응 성분들의 접촉을 최대한 보장할 수 있도록 하기 위해서, 불필요하게 많은 과량은 피해야 한다. The amount of base is not critical and usually 1 to 10 moles, in particular 1 to 5 moles, are used. If the bases are used simultaneously as solvents, the amount is generally proportional to the dissolution of the reaction components, and in order to reduce practical reasons and costs and to ensure maximum contact of the reaction components using a small reaction vessel, an unnecessary amount is required. Excess should be avoided.
반응 동안, 일산화탄소 압력은 화합물 VI를 기준으로 과량의 CO가 항상 존재하도록 조정된다. 바람직하게는, 실온에서의 일산화탄소 압력은 1 내지 250 bar, 특히 5 내지 150 bar이다.During the reaction, the carbon monoxide pressure is adjusted so that excess CO is always present based on compound VI. Preferably, the carbon monoxide pressure at room temperature is 1 to 250 bar, in particular 5 to 150 bar.
카르보닐화는 통상 20 내지 250 ℃, 특히 30 내지 150 ℃에서 연속적으로 또는 회분식으로 수행된다. 회분식 공정의 경우, 일산화탄소는 편의상 반응 혼합물 중으로 계속적으로 주입되어 일정한 압력을 유지시킨다.Carbonylation is usually carried out continuously or batchwise at 20 to 250 ° C, in particular 30 to 150 ° C. For batch processes, carbon monoxide is continuously injected into the reaction mixture for convenience to maintain a constant pressure.
출발 물질로서 사용되는 아릴할로겐 화합물 VII은 공지되어 있거나, 공지된 합성법을 적당한 결합하고, 상기 설명한 반응 순서에 의해서 쉽게 제조될 수 있다.The arylhalogen compounds VII used as starting materials are known or can be easily prepared by combining the known synthesis methods with suitable reaction sequences described above.
화학식 I의 벤조일 유도체의 목적 용도에 대하여, 적합한 치환체는 하기 라디칼과 같다:For the intended use of the benzoyl derivatives of formula I, suitable substituents are as follows:
L 및 M은 수소, L and M are hydrogen,
C1-C6-알킬, 예를 들어, 메틸, 에틸, 프로필, 1-메틸에틸, 부틸, 1-메틸프로필, 2-메틸프로필, 1,1-디메틸에틸, 펜틸, 1-메틸부틸, 2-메틸부틸, 3-메틸부틸, 1,1-디메틸프로필, 1,2-디메틸프로필, 2,2-디메틸프로필, 1-에틸프로필, 헥실, 1-메틸펜틸, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 1,1-디메틸부틸, 1,2-디메틸부틸, 1,3-디메틸부틸, 2,2-디메틸부틸, 2,3-디메틸부틸, 3,3-디메틸부틸, 1-에틸부틸, 1,1,2-트리메틸프로필, 1,2,2-트리메틸프로필, 1-에틸-1-메틸프로필 또는 1-에틸-2-메틸프로필,C 1 -C 6 -alkyl, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2 -Methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 Ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl,
특히 메틸, 에틸, 1-메틸에틸, 1-메틸프로필, 2-메틸프로필, 1,1-디메틸에틸 및 1,1-디메틸프로필;Especially methyl, ethyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl and 1,1-dimethylpropyl;
C2-C6-알케닐, 예를 들어, 2-프로페닐, 2-부테닐, 3-부테닐, 1-메틸-2-프로페닐, 2-메틸-2-프로페닐, 2-펜테닐, 3-펜테닐, 4-펜테닐, 3-메틸-2-부테닐, 1-메틸-2-부테닐, 2-메틸-2-부테닐, 1-메틸-3-부테닐, 2-메틸-4-부테닐, 3-메틸-3-부테닐, 1,1-디메틸-2-프로페닐, 1,2-디메틸-2-프로페닐, 1-에틸-2-프로페닐, 2-헥세닐, 3-헥세닐, 4-헥세닐, 5-헥세닐, 1-메틸-2-펜테닐, 2-메틸-2-펜테닐, 3-메틸-2-펜테닐, 4-메틸-2-펜테닐, 1-메틸-3-펜테닐, 2-메틸-3-펜테닐, 3-메틸-3-펜테닐, 4-메틸-3-펜테닐, 1-메틸-4-펜테닐, 2-메틸-4-펜테닐, 3-메틸-4-펜테닐, 4-메틸-4-펜테닐, 1,1-디메틸-2-부테닐, 1,1-디메틸-3-부테닐, 1,2-디메틸-2-부테닐, 1,3-디메틸-3-부테닐, 2,2-디메틸-3-부테닐, 2,3-디메틸-2-부테닐, 2,3-디메틸-3-부테닐, 1-에틸-2-부테닐, 1-에틸-3-부테닐, 2-에틸-2-부테닐, 2-에틸-3-부테닐, 1,1,2-트리메틸-2-프로페닐, 1-에틸-1-메틸-2-프로필 및 에틸-2-메틸-2-프로페닐,C 2 -C 6 -alkenyl, for example 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl , 3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl -4-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl , 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-phene Tenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl -4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2- Dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl , 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2- Phenyl, 1-ethyl-1-methyl-2-propyl and ethyl-2-methyl-2-propenyl,
특히 1-메틸-2-프로페닐, 1-메틸-2-부테닐, 1,1-디메틸-2-프로페닐 및 1,1-디메틸-2-부테닐;In particular 1-methyl-2-propenyl, 1-methyl-2-butenyl, 1,1-dimethyl-2-propenyl and 1,1-dimethyl-2-butenyl;
C2-C6-알키닐, 예를 들어, 프로파르길, 2-부티닐, 3-부티닐, 2-펜티닐, 3-펜티닐, 4-펜티닐, 1-메틸-3-부티닐, 2-메틸-3-부티닐, 1-메틸-2-부티닐, 1,1-디메틸-2-프로피닐, 1-에틸-2-프로피닐, 2-헥시닐, 3-헥시닐, 4-헥시닐, 5-헥시닐, 1-메틸-2-펜티닐, 1-메틸-3-펜티닐, 1-메틸-4-펜티닐, 3-메틸-4-펜티닐, 4-메틸-2-펜티닐, 1,1-디메틸-2-부티닐, 1,1-디메틸-3-부티닐, 1,2-디메틸-3-부티닐, 2,2-디메틸-3-부티닐, 1-에틸-2-부티닐, 1-에틸-3-부티닐, 2-에틸-3-부티닐 및 1-에틸-1-메틸-2-프로피닐;C 2 -C 6 -alkynyl, for example propargyl, 2-butynyl, 3-butynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl , 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4 -Hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2 -Pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1- Ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
C1-C4-알콕시, 예를 들어, 메톡시, 에톡시, n-프로폭시, 1-메틸에톡시, n-부톡시, 1-메틸프로폭시, 2-메틸프로폭시 및 1,1-디메틸에톡시,C 1 -C 4 -alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1- Dimethylethoxy,
특히, C1-C3-알콕시, 예를 들어, 메톡시, 에톡시 또는 i-프로폭시이며,In particular, C 1 -C 3 -alkoxy, for example methoxy, ethoxy or i-propoxy,
여기서, 이러한 기들은 불소, 염소, 브롬 및 요오드, 바람직하게는 불소 및 염소와 같은 1 내지 5 개의 할로겐 원자, 또는 상기 언급한 C1-C4-알콕시로 치환될 수 있다.These groups can here be substituted with fluorine, chlorine, bromine and iodine, preferably 1 to 5 halogen atoms such as fluorine and chlorine, or the abovementioned C 1 -C 4 -alkoxy.
상기 정의된 -(A)m-S(O)nR1기는 예를 들어,The-(A) m -S (O) n R 1 group defined above is for example
C1-C4-알킬티오, 예를 들어, 메틸티오, 에틸티오, n-프로필티오, 1-메틸에틸티오, n-부틸티오, 1-메틸프로필티오, 2-메틸프로필티오 및 1,1-디메틸에틸티오, 특히 메틸티오;C 1 -C 4 -alkylthio, for example methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1 Dimethylethylthio, in particular methylthio;
C1-C4-알킬술피닐, 예를 들어, 메틸술피닐, 에틸술피닐, n-프로필술피닐, 1-메틸에틸술피닐, n-부틸술피닐, 1-메틸프로필술피닐, 2-메틸프로필술피닐 및 1,1-디메틸에틸술피닐, 특히 메틸술피닐;C 1 -C 4 -alkylsulfinyl, for example methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2- Methylpropylsulfinyl and 1,1-dimethylethylsulfinyl, in particular methylsulfinyl;
C1-C4-알킬술포닐, 예를 들어, 메틸술포닐, 에틸술포닐, n-프로필술포닐, 1-메틸에틸술포닐, n-부틸술포닐, 1-메틸프로필술포닐, 2-메틸프로필술포닐 및 1,1-디메틸에틸술포닐, 특히 메틸술포닐;C 1 -C 4 -alkylsulfonyl, for example methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2- Methylpropylsulfonyl and 1,1-dimethylethylsulfonyl, in particular methylsulfonyl;
C1-C4-알콕시술포닐, 예를 들어, 메톡시술포닐, 에톡시술포닐, n-프로폭시술포닐, 1-메틸에톡시술포닐, n-부톡시술포닐, 1-메틸프로폭시술포닐, 2-메틸프로폭시술포닐 및 1,1-디메틸에톡시술포닐, 특히 메톡시술포닐;C 1 -C 4 -alkoxysulfonyl, for example methoxysulfonyl, ethoxysulfonyl, n-propoxysulfonyl, 1-methylethoxysulfonyl, n-butoxysulfonyl, 1-methylpropoxysulfonyl , 2-methylpropoxysulfonyl and 1,1-dimethylethoxysulfonyl, in particular methoxysulfonyl;
N-C1-C4-알킬술파모일, 예를 들어, N-메틸술파모일, N-에틸술파모일, N-n-프로필술파모일, N-1-메틸에틸술파모일, N-n-부틸술파모일, N-1-메틸프로필술파모일, N-2-메틸프로필술파모일 및 N-1,1-디메틸에틸술파모일, 특히 N-메틸술파모일;NC 1 -C 4 -alkylsulfamoyl, for example N-methylsulfamoyl, N-ethylsulfamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfamoyl, Nn-butylsulfamoyl, N-1 -Methylpropylsulfamoyl, N-2-methylpropylsulfamoyl and N-1,1-dimethylethylsulfamoyl, in particular N-methylsulfamoyl;
N-C1-C4-알킬술피나모일, 예를 들어, N-메틸술피나모일, N-에틸술피나모일, N-n-프로필술피나모일, N-1-메틸에틸술피나모일, N-n-부틸술피나모일, N-1-메틸프로필술피나모일, N-2-메틸프로필술피나모일 및 N-1,1-디메틸에틸술피나모일, 특히 N-메틸술피나모일;NC 1 -C 4 -alkylsulfinamoyl, for example N-methylsulfinamoyl, N-ethylsulfinayl, Nn-propylsulfinayl, N-1-methylethylsulfinayl, Nn-butylsulul Pinamoyl, N-1-methylpropylsulfinamoyl, N-2-methylpropylsulfinamoyl and N-1,1-dimethylethylsulfinamoyl, in particular N-methylsulfinamoyl;
디-C1-C4-알킬술파모일, 예를 들어, 디메틸술파모일, 디에틸술파모일, 디프로필술파모일, 디부틸술파모일, N-메틸-N-에틸술파모일, N-메틸-N-프로필술파모일, N-메틸-N-1-메틸에틸술파모일, N-메틸-N-1,1-디메틸에틸술파모일, 디-1-메틸에틸술파모일, N-에틸-N-1-메틸에틸술파모일 및 N-에틸-N-1,1-디메틸에틸술파모일, 특히 디메틸술파모일;Di-C 1 -C 4 -alkylsulfamoyl, for example dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N -Propylsulfamoyl, N-methyl-N-1-methylethylsulfamoyl, N-methyl-N-1,1-dimethylethylsulfamoyl, di-1-methylethylsulfamoyl, N-ethyl-N-1- Methylethylsulfamoyl and N-ethyl-N-1,1-dimethylethylsulfamoyl, in particular dimethylsulfamoyl;
디-C1-C4-알킬술피나모일, 예를 들어, 디메틸술피나모일, 디에틸술피나모일, 디프로필술피나모일, 디부틸술피나모일, N-메틸-N-에틸술피나모일, N-메틸-N-프로필술피나모일, N-메틸-N-1-메틸에틸술피나모일, N-메틸-N-1,1-디메틸에틸술피나모일, 디-1-메틸에틸술피나모일, N-에틸-N-1-메틸에틸술피나모일 및 N-에틸-N-1,1-디메틸에틸술피나모일, 특히 디메틸술피나모일;Di-C 1 -C 4 -alkylsulfinamoyl, for example dimethylsulfinamoyl, diethylsulfinayl, dipropylsulfinamoyl, dibutylsulfinamoyl, N-methyl-N-ethylsulfinamoyl , N-methyl-N-propylsulfinamoyl, N-methyl-N-1-methylethylsulfinamoyl, N-methyl-N-1,1-dimethylethylsulfinamoyl, di-1-methylethylsulfina Moyl, N-ethyl-N-1-methylethylsulfinamoyl and N-ethyl-N-1,1-dimethylethylsulfinamoyl, especially dimethylsulfinamoyl;
C1-C4-알킬술피닐옥시, 예를 들어, 메틸술피닐옥시, 에틸술피닐옥시, n-프로필술피닐옥시, 1-메틸에틸술피닐옥시, n-부틸술피닐옥시, 1-메틸프로필술피닐옥시, 2-메틸프로필술피닐옥시 및 1,1-디메틸에틸술피닐옥시, 특히 메틸술피닐옥시;C 1 -C 4 -alkylsulfinyloxy, for example methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methyl Propylsulfinyloxy, 2-methylpropylsulfinyloxy and 1,1-dimethylethylsulfinyloxy, especially methylsulfinyloxy;
C1-C4-알킬술포닐옥시, 예를 들어, 메틸술포닐옥시, 에틸술포닐옥시, n-프로필술포닐옥시, 1-메틸에틸술포닐옥시, n-부틸술포닐옥시, 1-메틸프로필술포닐옥시, 2-메틸프로필술포닐옥시 및 1,1-디메틸에틸술포닐옥시, 특히 메틸술포닐옥시;C 1 -C 4 -alkylsulfonyloxy, for example methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methyl Propylsulfonyloxy, 2-methylpropylsulfonyloxy and 1,1-dimethylethylsulfonyloxy, especially methylsulfonyloxy;
C1-C4-알킬술피닐아미노, 예를 들어, 메틸술피닐아미노, 에틸술피닐아미노, n-프로필술피닐아미노, 1-메틸에틸술피닐아미노, n-부틸술피닐아미노, 1-메틸프로필술피닐아미노, 2-메틸프로필술피닐아미노 및 1,1-디메틸에틸술피닐아미노, 특히 메틸술피닐아미노;C 1 -C 4 -alkylsulfinylamino, for example methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methyl Propylsulfinylamino, 2-methylpropylsulfinylamino and 1,1-dimethylethylsulfinylamino, especially methylsulfinylamino;
C1-C4-알킬술포닐아미노, 예를 들어, 메틸술포닐아미노, 에틸술포닐아미노, n-프로필술포닐아미노, 1-메틸에틸술포닐아미노, n-부틸술포닐아미노, 1-메틸프로필술포닐아미노, 2-메틸프로필술포닐아미노 및 1,1-디메틸에틸술포닐아미노, 특히 메틸술포닐아미노;C 1 -C 4 -alkylsulfonylamino, for example methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methyl Propylsulfonylamino, 2-methylpropylsulfonylamino and 1,1-dimethylethylsulfonylamino, especially methylsulfonylamino;
N-C1-C4-알킬술피닐-N-메틸아미노, 예를 들어, N-메틸술피닐-N-메틸아미노, N-에틸술피닐-N-메틸아미노, N-n-프로필술피닐-N-메틸아미노, N-1-메틸에틸술피닐-N-메틸아미노, N-n-부틸술피닐-N-메틸아미노, N-1-메틸프로필술피닐-N-메틸아미노, N-2-메틸프로필술피닐-N-메틸아미노 및 N-1,1-디메틸에틸술피닐-N-메틸아미노, 특히 N-메틸술피닐-N-메틸아미노;NC 1 -C 4 -alkylsulfinyl-N-methylamino, for example N-methylsulfinyl-N-methylamino, N-ethylsulfinyl-N-methylamino, Nn-propylsulfinyl-N-methyl Amino, N-1-methylethylsulfinyl-N-methylamino, Nn-butylsulfinyl-N-methylamino, N-1-methylpropylsulfinyl-N-methylamino, N-2-methylpropylsulfinyl- N-methylamino and N-1,1-dimethylethylsulfinyl-N-methylamino, in particular N-methylsulfinyl-N-methylamino;
N-C1-C4-알킬술피닐-N-에틸아미노, 예를 들어, N-메틸술피닐-N-에틸아미노, N-에틸술피닐-N-에틸아미노, N-n-프로필술피닐-N-에틸아미노, N-1-메틸에틸술피닐-N-에틸아미노, N-n-부틸술피닐-N-에틸아미노, N-1-메틸프로필술피닐-N-에틸아미노, N-2-메틸프로필술피닐-N-에틸아미노 및 N-1,1-디메틸에틸술피닐-N-에틸아미노, 특히 N-메틸술피닐-N-에틸아미노;NC 1 -C 4 -alkylsulfinyl-N-ethylamino, for example N-methylsulfinyl-N-ethylamino, N-ethylsulfinyl-N-ethylamino, Nn-propylsulfinyl-N-ethyl Amino, N-1-methylethylsulfinyl-N-ethylamino, Nn-butylsulfinyl-N-ethylamino, N-1-methylpropylsulfinyl-N-ethylamino, N-2-methylpropylsulfinyl- N-ethylamino and N-1,1-dimethylethylsulfinyl-N-ethylamino, in particular N-methylsulfinyl-N-ethylamino;
N-C1-C4-알킬술포닐-N-메틸아미노, 예를 들어, N-메틸술포닐-N-메틸아미노, N-에틸술포닐-N-메틸아미노, N-n-프로필술포닐-N-메틸아미노, N-1-메틸에틸술포닐-N-메틸아미노, N-n-부틸술포닐-N-메틸아미노, N-1-메틸프로필술포닐-N-메틸아미노, N-2-메틸프로필술포닐-N-메틸아미노 및 N-1,1-디메틸에틸술포닐-N-메틸아미노, 특히 N-메틸술포닐-N-메틸아미노;NC 1 -C 4 -alkylsulfonyl-N-methylamino, for example N-methylsulfonyl-N-methylamino, N-ethylsulfonyl-N-methylamino, Nn-propylsulfonyl-N-methyl Amino, N-1-methylethylsulfonyl-N-methylamino, Nn-butylsulfonyl-N-methylamino, N-1-methylpropylsulfonyl-N-methylamino, N-2-methylpropylsulfonyl- N-methylamino and N-1,1-dimethylethylsulfonyl-N-methylamino, in particular N-methylsulfonyl-N-methylamino;
N-C1-C4-알킬술포닐-N-에틸아미노, 예를 들어, N-메틸술포닐-N-에틸아미노, N-에틸술포닐-N-에틸아미노, N-n-프로필술포닐-N-에틸아미노, N-1-메틸에틸술포닐-N-에틸아미노, N-n-부틸술포닐-N-에틸아미노, N-1-메틸프로필술포닐-N-에틸아미노, N-2-메틸프로필술포닐-N-에틸아미노 및 N-1,1-디메틸에틸술포닐-N-에틸아미노, 특히 N-메틸술포닐-N-에틸아미노;NC 1 -C 4 -alkylsulfonyl-N-ethylamino, for example N-methylsulfonyl-N-ethylamino, N-ethylsulfonyl-N-ethylamino, Nn-propylsulfonyl-N-ethyl Amino, N-1-methylethylsulfonyl-N-ethylamino, Nn-butylsulfonyl-N-ethylamino, N-1-methylpropylsulfonyl-N-ethylamino, N-2-methylpropylsulfonyl- N-ethylamino and N-1,1-dimethylethylsulfonyl-N-ethylamino, in particular N-methylsulfonyl-N-ethylamino;
C1-C4-할로알킬티오, 예를 들어, 클로로메틸티오, 디클로로메틸티오, 트리클로로메틸티오, 플루오로메틸티오, 디플루오로메틸티오, 트리플루오로메틸티오, 클로로플루오로메틸티오, 클로로디플루오로메틸티오, 1-플루오로에틸티오, 2-플루오로에틸티오, 2,2-디플루오로에틸티오, 2,2,2-트리플루오로에틸티오, 2-클로로-2,2-디플루오로에틸티오, 2,2-디클로로-2-플루오로에틸티오, 2,2,2-트리클로로에틸티오 및 펜타플루오로에틸티오, 특히 트리플루오로메틸티오이다.C 1 -C 4 -haloalkylthio, for example chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, Chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2,2 -Difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio, in particular trifluoromethylthio.
상기 정의한 -(A)m-CO-R2 기는 예를 들어,The-(A) m -CO-R 2 group defined above is, for example,
C1-C4-알킬카르보닐, 예를 들어, 메틸카르보닐, 에틸카르보닐, n-프로필카르보닐, 1-메틸에틸카르보닐, n-부틸카르보닐, 1-메틸프로필카르보닐, 2-메틸프로필카르보닐 및 1,1-디메틸에틸카르보닐, 특히 메틸카르보닐;C 1 -C 4 -alkylcarbonyl, for example methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2- Methylpropylcarbonyl and 1,1-dimethylethylcarbonyl, especially methylcarbonyl;
C1-C4-알콕시카르보닐, 예를 들어, 메톡시카르보닐, 에톡시카르보닐, n-프로폭시카르보닐, 1-메틸에톡시카르보닐, n-부톡시카르보닐, 1-메틸프로폭시카르보닐, 2-메틸프로폭시카르보닐 및 1,1-디메틸에톡시카르보닐, 특히 메톡시카르보닐;C 1 -C 4 -alkoxycarbonyl, for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methylprop Foxoxycarbonyl, 2-methylpropoxycarbonyl and 1,1-dimethylethoxycarbonyl, in particular methoxycarbonyl;
N-C1-C4-알킬카르바모일, 예를 들어, N-메틸카르바모일, N-에틸카르바모일, N-n-프로필카르바모일, N-1-메틸에틸카르바모일, N-n-부틸카르바모일, N-1-메틸프로필카르바모일, N-2-메틸프로필카르바모일 및 N-1,1-디메틸에틸카르바모일, 특히 N-메틸카르바모일;NC 1 -C 4 -alkylcarbamoyl, for example N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarba Barmoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl and N-1,1-dimethylethylcarbamoyl, in particular N-methylcarbamoyl;
디-C1-C4-알킬카르바모일, 예를 들어, 디메틸카르바모일, 디에틸카르바모일, 디프로필카르바모일, 디부틸카르바모일, N-메틸-N-에틸카르바모일, N-메틸-N-프로필카르바모일, N-메틸-N-1-메틸에틸카르바모일, N-메틸-N-1,1-디메틸에틸카르바모일, 디-1-메틸에틸카르바모일, N-에틸-N-1-메틸에틸카르바모일 및 N-에틸-N-1,1-디메틸에틸카르바모일, 특히 디메틸카르바모일;Di-C 1 -C 4 -alkylcarbamoyl, for example dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl , N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl-N-1,1-dimethylethylcarbamoyl, di-1-methylethylcarba Moyl, N-ethyl-N-1-methylethylcarbamoyl and N-ethyl-N-1,1-dimethylethylcarbamoyl, in particular dimethylcarbamoyl;
C1-C4-알킬카르보닐옥시, 예를 들어, 메틸카르보닐옥시, 에틸카르보닐옥시, n-프로필카르보닐옥시, 1-메틸에틸카르보닐옥시, n-부틸카르보닐옥시, 1-메틸프로필카르보닐옥시, 2-메틸프로필카르보닐옥시 및 1,1-디메틸에틸카르보닐옥시, 특히 메틸카르보닐옥시;C 1 -C 4 -alkylcarbonyloxy, for example methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methyl Propylcarbonyloxy, 2-methylpropylcarbonyloxy and 1,1-dimethylethylcarbonyloxy, especially methylcarbonyloxy;
C1-C4-알킬카르보닐아미노, 예를 들어, 메틸카르보닐아미노, 에틸카르보닐아미노, n-프로필카르보닐아미노, 1-메틸에틸카르보닐아미노, n-부틸카르보닐아미노, 1-메틸프로필카르보닐아미노, 2-메틸프로필카르보닐아미노 및 1,1-디메틸에틸카르보닐아미노, 특히 메틸카르보닐아미노;C 1 -C 4 -alkylcarbonylamino, for example methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, 1-methylethylcarbonylamino, n-butylcarbonylamino, 1-methyl Propylcarbonylamino, 2-methylpropylcarbonylamino and 1,1-dimethylethylcarbonylamino, especially methylcarbonylamino;
N-C1-C4-알킬카르보닐-N-메틸아미노, 예를 들어, N-메틸카르보닐-N-메틸아미노, N-에틸카르보닐-N-메틸아미노, N-n-프로필카르보닐-N-메틸아미노, N-1-메틸에틸카르보닐-N-메틸아미노, N-n-부틸카르보닐-N-메틸아미노, N-1-메틸프로필카르보닐-N-메틸아미노, N-2-메틸프로필카르보닐-N-메틸아미노 및 N-1,1-디메틸에틸카르보닐-N-메틸아미노, 특히 N-메틸카르보닐-N-메틸아미노이다.NC 1 -C 4 -alkylcarbonyl-N-methylamino, for example N-methylcarbonyl-N-methylamino, N-ethylcarbonyl-N-methylamino, Nn-propylcarbonyl-N-methyl Amino, N-1-methylethylcarbonyl-N-methylamino, Nn-butylcarbonyl-N-methylamino, N-1-methylpropylcarbonyl-N-methylamino, N-2-methylpropylcarbonyl- N-methylamino and N-1,1-dimethylethylcarbonyl-N-methylamino, in particular N-methylcarbonyl-N-methylamino.
X는 예를 들어, CH2, CH(CH3), C((CH3)2), CH(C2H5), C((C2H5)2) CH(C6H5), CH2-CH2, CH2-CH(CH3), CH2-C((CH3)2), CH(CH3)-CH(CH3), CH(CH3)-C((CH3)2), C((CH3)2)-C((CH3)2), CH2-CH(C2H5), CH2-C((C2H5)2), CH(C2H5)-CH(C2H5), CH(C2H5)-C((C2H5)2), C((C2H5)2)-C((C2H5)2), CH2-CH(C3H7), CH2-CH(iC3H7), CH2-CH(C4H9), CH2-CH(iC4H9), CH2-CH(Br), CH2-C((Br)2), CH(Br)-CH(Br), CH((Br)2)-C((Br)2), CH2-CH(Cl), CH2-C((Cl)2), CH(Cl)-C((Cl)2), C((Cl)2)-C((Cl)2), CH2-CH(C6H5), CH(C6H5)-CH(C6H5), CH2-CH(p-NO2C6H5), CH=CH, C(CH3)=CH, C(CH3)=CCH3, CH=CBr, CH=CCl, CBr=CBr, CCl=CCl, CH=C(OCH3), CH=C(C6H5), C(C6H5)=C(C6H5), C(C2H5)=CH, C(C2H5)=C(C2H5), CH=C(C3H5), CH=C(C4H7), CH2-CH=CH, CH(CH3)-CH=CH, C((CH3)2)-CH=CH, CH2-CH=C(CH3), CH2-C(CH3)=CH, CH2-C(CH3)=C(CH3), CH(CH3)-C(CH3)=C(CH3), C((CH3)2)-C(CH3)=C(CH3), N-H, N-CH3, N-C2H5, N-C3H7, N-C4H9, N-iC3H7, N-OCH3, N-OC2H5, N-CH2C6H5, N-C6H5이다.X is for example CH 2 , CH (CH 3 ), C ((CH 3 ) 2 ), CH (C 2 H 5 ), C ((C 2 H 5 ) 2 ) CH (C 6 H 5) , CH 2 -CH 2 , CH 2 -CH (CH 3 ), CH 2 -C ((CH 3 ) 2 ), CH (CH 3 ) -CH (CH 3 ), CH (CH 3 ) -C ((CH 3) ) 2 ), C ((CH 3 ) 2 ) -C ((CH 3 ) 2 ), CH 2 -CH (C 2 H 5 ), CH 2 -C ((C 2 H 5 ) 2 ), CH (C 2 H 5 ) -CH (C 2 H 5 ), CH (C 2 H 5 ) -C ((C 2 H 5 ) 2 ), C ((C 2 H 5 ) 2 ) -C ((C 2 H 5 ) 2 ), CH 2 -CH (C 3 H 7 ), CH 2 -CH (iC 3 H 7 ), CH 2 -CH (C 4 H 9 ), CH 2 -CH (iC 4 H 9 ), CH 2 -CH (Br), CH 2 -C ((Br) 2 ), CH (Br) -CH (Br), CH ((Br) 2 ) -C ((Br) 2 ), CH 2 -CH (Cl) , CH 2 -C ((Cl) 2 ), CH (Cl) -C ((Cl) 2 ), C ((Cl) 2 ) -C ((Cl) 2 ), CH 2 -CH (C 6 H 5 ), CH (C 6 H 5 ) -CH (C 6 H 5 ), CH 2 -CH (p-NO 2 C 6 H 5 ), CH = CH, C (CH 3 ) = CH, C (CH 3 ) = CCH 3 , CH = CBr, CH = CCl, CBr = CBr, CCl = CCl, CH = C (OCH 3 ), CH = C (C 6 H 5 ), C (C 6 H 5 ) = C (C 6 H 5 ), C (C 2 H 5 ) = CH, C (C 2 H 5 ) = C (C 2 H 5 ), CH = C (C 3 H 5 ), CH = C (C 4 H 7 ), CH 2 -CH = CH, CH (CH 3 ) -CH = CH, C ((CH 3 ) 2 ) -CH = CH, CH 2 -CH = C (CH 3 ), CH 2 -C (CH 3 ) = CH, CH 2 -C (CH 3 ) = C (CH 3 ), CH (CH 3 ) -C (CH 3 ) = C (CH 3 ), C ((CH 3 ) 2 ) -C (CH 3 ) = C (CH 3 ), NH, N-CH 3 , NC 2 H 5 , NC 3 H 7 , NC 4 H 9 , N-iC 3 H 7 , N-OCH 3 , N-OC 2 H 5 , N-CH 2 C 6 H 5 , NC 6 H 5 .
Y는 예를 들어, C=O, CH-OH, CH-OCH3, CH-OC2H5, CH-OC3H7, CH-OiPr, CH-OC4H9, CH-OiBu, CH-OC5H11, CH-OC6H13, CH-OC6H5, C(CH3)-OCH3, C(CH3)-OC2H5, C(CH3)-OC3H7, C(CH3)-OC4H9, C(CH3)-OiPr, C(CH3)-OiBu, C(CH3)-OtBu, C(CH3)-OPh, CH2, CH(CH3), C((CH3)2), C=N-CH3, C=N-C2H5, C=N-C3H7, C=N-C4H9, C=N-iC4H9, C=N-tC4H9, C=N-iPr, C=N-OCH3, C=N-OC2H5, C=N-OC3H7, C=N-OC4H9, C=N-OiC4H9, C=N-OtC4H9, C=N-OCH2CH=CH2, C=N-OCH(CH3)CH=CH2, C=N-OCH2CH=CHCH3, C=N-OCH2CH=C(CH3)2, C=N-OCH2CH=CHBr, C=N-OCH2CH=CHCl, C=N-OCH2CH=CHC2H5, C=N-OCH2C≡CH, C=N-OCH2C≡CCH3, C=N-OCH2C6H5, CH-NH(OCH3), CH-NH(OC2H5), CH-NH(OiPr), CH-NH(OnPr), CH-NH(OC6H5), CH-NCH3(OCH3), CH-NCH3(OC2H5), CH-NCH3(OiPr), CH-NCH3(OnPr), CH-NCH3(OC6H5), CH-NH(CH3), CH-NH(C2H5), CH-NH(C3H7), CH-NH(C4H9), CH-NH(iPr), CH-NH(iBu), CH-NH(tBu), CH-NH(C6H5), CH-N(CH3)2, CH-NCH3(C2H5), CH-NCH3(C3H7), CH-NCH3(C4H9), CH-NCH3(iPr), CH-NCH3(iBu), C=N-NH2, C=N-NHCH3, C=N-N((CH3)2), C=N-NH(C2H5), C=N-NCH3(C2H5), C=N-N((C2H5)2), CH-SCH3, CH-SC2H5, CH-SC3H7, CH-SC4H9, CH-SPr, CH-SiBu, CH-SH, C(CH3)-SCH3, C(CH3)-SC2H5, C(CH3)-SC3H7, 1,3-디옥사닐, 1,3-디옥솔라닐, 5,5-디메틸-1,3-디옥사닐이다.Y is for example C = O, CH-OH, CH-OCH 3 , CH-OC 2 H 5 , CH-OC 3 H 7 , CH-OiPr, CH-OC 4 H 9 , CH-OiBu, CH- OC 5 H 11 , CH-OC 6 H 13 , CH-OC 6 H 5 , C (CH 3 ) -OCH 3 , C (CH 3 ) -OC 2 H 5 , C (CH 3 ) -OC 3 H 7 , C (CH 3 ) -OC 4 H 9 , C (CH 3 ) -OiPr, C (CH 3 ) -OiBu, C (CH 3 ) -OtBu, C (CH 3 ) -OPh, CH 2 , CH (CH 3 ), C ((CH 3 ) 2 ), C = N-CH 3 , C = NC 2 H 5 , C = NC 3 H 7 , C = NC 4 H 9 , C = N-iC 4 H 9 , C = N-tC 4 H 9 , C = N-iPr, C = N-OCH 3 , C = N-OC 2 H 5 , C = N-OC 3 H 7 , C = N-OC 4 H 9 , C = N -OiC 4 H 9 , C = N-OtC 4 H 9 , C = N-OCH 2 CH = CH 2 , C = N-OCH (CH 3 ) CH = CH 2 , C = N-OCH 2 CH = CHCH 3 , C = N-OCH 2 CH = C (CH 3 ) 2 , C = N-OCH 2 CH = CHBr, C = N-OCH 2 CH = CHCl, C = N-OCH 2 CH = CHC 2 H 5 , C = N-OCH 2 C≡CH, C = N-OCH 2 C≡CCH 3 , C = N-OCH 2 C 6 H 5 , CH-NH (OCH 3 ), CH-NH (OC 2 H 5 ), CH -NH (OiPr), CH-NH (OnPr), CH-NH (OC 6 H 5 ), CH-NCH 3 (OCH 3 ), CH-NCH 3 (OC 2 H 5 ), CH-NCH 3 (OiPr) , CH-NCH 3 (OnPr), CH-NCH 3 (OC 6 H 5 ), CH-NH (CH 3 ), CH-NH (C 2 H 5 ), CH-NH (C 3 H 7 ), CH- NH (C 4 H 9 ), CH-NH (iPr), CH-NH (iBu), CH-NH (tBu), CH-NH (C 6 H 5 ), CH-N (CH 3 ) 2 , CH-NCH 3 (C 2 H 5 ), CH-NCH 3 (C 3 H 7 ), CH-NCH 3 (C 4 H 9 ), CH-NCH 3 (iPr), CH-NCH 3 (iBu), C = N-NH 2 , C = N-NHCH 3 , C = NN ((CH 3 ) 2 ), C = N-NH (C 2 H 5 ), C = N-NCH 3 (C 2 H 5 ), C = NN ((C 2 H 5 ) 2 ), CH-SCH 3 , CH-SC 2 H 5 , CH-SC 3 H 7 , CH-SC 4 H 9 , CH-SPr , CH-SiBu, CH-SH, C (CH 3 ) -SCH 3 , C (CH 3 ) -SC 2 H 5 , C (CH 3 ) -SC 3 H 7 , 1,3-dioxanyl, 1, 3-dioxolanyl, 5,5-dimethyl-1,3-dioxanyl.
바람직한 벤조일 유도체는 화학식 Ia의 화합물이다.Preferred benzoyl derivatives are compounds of formula (Ia).
상기 식에서, Where
L은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-알킬티오, C1-C4-할로알킬, C1-C4-할로알콕시, C1-C4-할로알킬티오, C1-C4-알킬술포닐, 할로겐, 니트로 또는 시아노이며,L is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1- C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkylsulfonyl, halogen, nitro or cyano,
M은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-알킬티오, C1-C4-할로알킬, C1-C4-할로알콕시, C1-C4-할로알킬티오, C1-C4-알킬술포닐, 할로겐, 니트로 또는 시아노이고,M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1- C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkylsulfonyl, halogen, nitro or cyano,
Q, X, n 및 Y는 상기 화합물 I에 대하여 정의된 의미를 가지며, Q, X, n and Y have the meanings defined for Compound I above,
Y가 C=O인 경우, X는 NR23이 아니다.When Y is C═O, X is not NR 23 .
또한, 바람직한 벤조일 유도체는 화학식 Ib의 화합물이다.Preferred benzoyl derivatives are also compounds of formula Ib.
상기 식에서, Where
L은 C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이며,L is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 Haloalkoxy, halogen, nitro or cyano,
M은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이고,M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1- C 4 -haloalkoxy, halogen, nitro or cyano,
Q, X, n 및 Y는 상기 화합물 I에 대하여 정의된 의미를 가지며, Q, X, n and Y have the meanings defined for Compound I above,
Y가 C=O인 경우, X는 NR23이 아니다.When Y is C═O, X is not NR 23 .
또한, 바람직한 벤조일 유도체는 L 및 M 라디칼이 수소, 메틸, 메톡시, 염소, 시아노, 니트로 또는 트리플루오로메틸인 화학식 I의 화합물이다. Preferred benzoyl derivatives are also compounds of formula I, wherein the L and M radicals are hydrogen, methyl, methoxy, chlorine, cyano, nitro or trifluoromethyl.
바람직한 벤조일 유도체는 화학식 Ic의 화합물이다.Preferred benzoyl derivatives are compounds of formula (Ic).
상기 식에서, Where
L은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이며,L is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1- C 4 -haloalkoxy, halogen, nitro or cyano,
M은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이고,M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1- C 4 -haloalkoxy, halogen, nitro or cyano,
Q, n, Y 및 R21, R22, R12 및 R13은 상기 화합물 I에 대하여 정의된 의미를 갖는다.Q, n, Y and R 21 , R 22 , R 12 and R 13 have the meanings defined for compound I above.
마찬가지로, 바람직한 벤조일 유도체는 화학식 Id의 화합물이다.Likewise, preferred benzoyl derivatives are compounds of formula Id.
상기 식에서, Where
L은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이며,L is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1- C 4 -haloalkoxy, halogen, nitro or cyano,
M은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이고,M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1- C 4 -haloalkoxy, halogen, nitro or cyano,
Q, n, Y 및 R12과 R13은 상기 화합물 I에 대하여 정의된 의미를 갖는다.Q, n, Y and R 12 and R 13 have the meanings defined for compound I above.
또한, 바람직한 벤조일 유도체는 화학식 Ie의 화합물이다.Preferred benzoyl derivatives are also compounds of formula (Ie).
상기 식에서, Where
L은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이며,L is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1- C 4 -haloalkoxy, halogen, nitro or cyano,
M은 수소, C1-C6-알킬, C2-C6-알케닐, C2-C6-알키닐, C1-C4-알콕시, C1-C4-할로알킬, C1-C4-할로알콕시, 할로겐, 니트로 또는 시아노이고,M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1- C 4 -haloalkoxy, halogen, nitro or cyano,
Q, n, Y, R12 및 R13은 상기 화합물 I에 대하여 정의된 의미를 갖는다.Q, n, Y, R 12 and R 13 have the meanings defined for Compound I above.
또한, 바람직한 벤조일 유도체는 n이 1 또는 2이고 Y가 CR7-OR8 (여기서, R7 및 R8은 상기 화합물 I에 대하여 정의된 의미를 가짐)인 화학식 I의 화합물이다.Preferred benzoyl derivatives are also compounds of formula I, wherein n is 1 or 2 and Y is CR 7 -OR 8 , wherein R 7 and R 8 have the meanings defined for compound I above.
<표 1a>TABLE 1a
하기 화학식의 화합물Compound of formula
<표 1b>TABLE 1b
<표 1c>TABLE 1c
<표 1d>TABLE 1D
<표 1e>TABLE 1e
<표 2a>TABLE 2a
하기 화학식의 화합물Compound of formula
X의 R12 라디칼과 Y의 R7 라디칼은 결합을 형성한다.The R 12 radicals of X and the R 7 radicals of Y form a bond.
<표 2b>TABLE 2b
<표 3a>TABLE 3a
하기 화학식의 화합물Compound of formula
<표 3b>TABLE 3b
<표 3c>TABLE 3c
<표 3d>Table 3d
<표 3e>TABLE 3e
< 3f><3f>
< 3g><3g>
< 3h><3h>
<표 4a>TABLE 4a
하기 화학식의 화합물Compound of formula
<표 4b>TABLE 4b
<표 4c>TABLE 4c
<표 4d>TABLE 4d
<표 4e>TABLE 4e
<표 4f>TABLE 4f
<표 4g><Table 4g>
<표 4h>TABLE 4h
<표 4i>TABLE 4i
<표 4j>TABLE 4j
<표 4k><Table 4k>
<표 4l>TABLE 4L
<표 4m><Table 4m>
<표 4n>TABLE 4n
<표 4o>TABLE 4o
<표 4p>TABLE 4p
<표 4q>TABLE 4q
<표 4r>TABLE 4r
<표 4s>TABLE 4S
<표 4t><Table 4t>
<표 4u>TABLE 4u
<표 4v>TABLE 4v
<표 4w>TABLE 4W
<표 4x>TABLE 4x
<표 4y>TABLE 4y
<표 4z>TABLE 4z
<표 4aa>Table 4aa
<표 4ab>TABLE 4ab
<표 4ac>TABLE 4ac
<표 4ad>TABLE 4ad
<표 4ae>TABLE 4ae
<표 4af><Table 4af>
<표 4ag><Table 4ag>
<표 4ah><Table 4ah>
<표 4ai><Table 4ai>
<표 4aj>Table 4aj
<표 4ak><Table 4ak>
<표 4al><Table 4al>
<표 4am><Table 4am>
<표 4an><Table 4an>
<표 4ao><Table 4ao>
<표 4ap><Table 4ap>
<표 4aq>TABLE 4aq
<표 4ar><Table 4ar>
<표 4as>TABLE 4as
<표 4at><Table 4at>
<표 4au><Table 4au>
<표 4av><Table 4av>
<표 4aw><Table 4aw>
<표 4ax><Table 4ax>
<표 4ay><Table 4ay>
<표 4az><Table 4az>
<표 4ba><Table 4ba>
<표 4bb><Table 4bb>
<표 4bc><Table 4bc>
<표 4bd>Table 4bd
<표 4be><Table 4be>
<표 4bf>TABLE 4bf
<표 4bg>Table 4bg
<표 4bh><Table 4bh>
<표 4bi>Table 4bi
<표 4bj><Table 4bj>
<표 4bk><Table 4bk>
<표 4bl>TABLE 4bl
<표 4bm><Table 4bm>
<표 4bn>Table 4bn
<표 4bo><Table 4bo>
<표 4bp>Table 4 bp
<표 4bq>TABLE 4bq
<표 4br><Table 4br>
<표 4bs>TABLE 4bs
<표 4bt><Table 4bt>
<표 4bu><Table 4bu>
<표 4bv>TABLE 4bv
<표 4bw><Table 4bw>
<표 4bx>TABLE 4bx
<표 4by>Table 4by
<표 4bz><Table 4bz>
<표 4ca><Table 4ca>
<표 4cb>TABLE 4cb
<표 4cc><Table 4cc>
<표 4cd><Table 4cd>
<표 4ce><Table 4ce>
<표 4cf>TABLE 4cf
<표 4cg>Table 4cg
<표 4ch><Table 4ch>
<표 4ci>TABLE 4ci
<표 4cj>Table 4cj
<표 4ck>Table 4ck
<표 4cl><Table 4cl>
<표 4cm><Table 4cm>
<표 4cn><Table 4cn>
<표 4co><Table 4co>
<표 4cp><Table 4cp>
<표 4cq>TABLE 4cq
<표 4cr><Table 4cr>
<표 4cs><Table 4cs>
<표 4ct><Table 4ct>
<표 4cu><Table 4cu>
<표 4cv><Table 4cv>
<표 4cw>TABLE 4cw
<표 4cx>Table 4cx
<표 4cy>TABLE 4cy
<표 4cz><Table 4cz>
<표 4da><Table 4da>
<표 4db><Table 4db>
<표 4dc>Table 4dc
<표 4dd>TABLE 4dd
<표 4de>TABLE 4de
<표 4df><Table 4df>
<표 4dg><Table 4dg>
<표 4dh><Table 4dh>
<표 4di><Table 4di>
<표 4dj>TABLE 4dj
<표 4dk><Table 4dk>
<표 4dl><Table 4dl>
<표 4dm><Table 4dm>
<표 4dn><Table 4dn>
<표 4do><Table 4do>
<표 4dp><Table 4dp>
<표 4dq>TABLE 4dq
<표 4dr>TABLE 4dr
<표 4ds>TABLE 4ds
<표 4dt>TABLE 4dt
<표 4du><Table 4du>
<표 4dv>TABLE 4dv
<표 4dw><Table 4dw>
<표 4dx>TABLE 4dx
<표 4dy><Table 4dy>
<표 4dz><Table 4dz>
<표 4ea><Table 4ea>
<표 4eb><Table 4eb>
<표 4ec>TABLE 4ec
<표 4ed>Table 4ed
<표 4ee><Table 4ee>
<표 4ef>TABLE 4ef
<표 4eg><Table 4eg>
<표 4eh><Table 4eh>
<표 4ei><Table 4ei>
<표 4ej><Table 4ej>
<표 5a>TABLE 5a
하기 화학식의 화합물Compound of formula
X의 R12 라디칼과 Y의 R7 라디칼은 결합을 형성한다.The R 12 radicals of X and the R 7 radicals of Y form a bond.
<표 5b>TABLE 5b
<표 5c>TABLE 5c
<표 5d>TABLE 5d
<표 6a>TABLE 6a
하기 화학식의 화합물Compound of formula
<표 6b>TABLE 6b
<표 6c>TABLE 6c
<표 6d>Table 6d
<표 6e>TABLE 6e
<표 6f>TABLE 6f
<표 6g>Table 6g
<표 6h>TABLE 6h
<표 6i>TABLE 6i
<표 6j>TABLE 6j
<표 6k><Table 6k>
<표 6l>TABLE 6L
<표 6m><Table 6m>
<표 6n>TABLE 6n
<표 6o>Table 6o
<표 6p>TABLE 6p
<표 6q>TABLE 6q
<표 6r>TABLE 6r
<표 6s>TABLE 6S
<표 6t>TABLE 6t
<표 6u>TABLE 6u
<표 6v>TABLE 6v
<표 6w>TABLE 6W
<표 6x>TABLE 6x
<표 7a>TABLE 7a
하기 화학식의 화합물Compound of formula
R7 및 R23 라디칼은 결합을 형성한다.R 7 and R 23 radicals form a bond.
<표 7b>TABLE 7b
<표 8a>TABLE 8a
하기 화학식의 화합물Compound of formula
<표 8b>TABLE 8b
<표 9a>TABLE 9a
하기 화학식의 화합물Compound of formula
<표 9b>TABLE 9b
<표 9c>TABLE 9c
<표 10a>TABLE 10a
하기 화학식의 화합물Compound of formula
<표 10b>TABLE 10b
<표 10c>TABLE 10c
<표 11a>TABLE 11a
하기 화학식의 화합물Compound of formula
<표 11b>TABLE 11b
<표 11c>TABLE 11c
<표 11d>TABLE 11D
<표 11e>TABLE 11e
<제조예><Production example>
A) 출발 물질 및 중간체의 제조A) Preparation of Starting Materials and Intermediates
1. 3-티오-2-메틸벤조산 1.3-thio-2-methylbenzoic acid
3-아미노-2-메틸벤조산 100 g (0.66 몰)을 얼음 270 g 및 농축된 염산 127 ml과 함께 먼저 투입하였다. 이어서, 물 270 ml 중의 아질산나트륨 45.7 g (0.66 몰)을 0 내지 10 ℃에서 적가하였다. 100 g (0.66 mol) of 3-amino-2-methylbenzoic acid were first charged with 270 g of ice and 127 ml of concentrated hydrochloric acid. Then 45.7 g (0.66 mol) of sodium nitrite in 270 ml of water were added dropwise at 0 to 10 ° C.
두 번째 용기에 탄산나트륨 84.2 g (0.79 몰) 및 칼륨 메틸크산테이트 106 g (0.66 몰)을 물 450 ml 중에 용해시키고 60 내지 70 ℃로 가열하였다. 디아조늄 용액을 조심스럽게 적가하였다. 후속해서, 혼합물을 1 시간 동안 교반하였다. 물 270 ml 중의 수산화나트륨 106 g (2.65 몰)을 가하고, 그 혼합물을 2 시간 동안 교반한 후, 용액을 염산을 사용하여 산성화시키고 생성되는 침전물을 흡입으로 여과하였다. 고체를 물로 세척하고 건조시켰다. In a second vessel 84.2 g (0.79 mole) of sodium carbonate and 106 g (0.66 mole) of potassium methylxanthate were dissolved in 450 ml of water and heated to 60-70 ° C. Diazonium solution was carefully added dropwise. Subsequently, the mixture was stirred for 1 hour. 106 g (2.65 mol) of sodium hydroxide in 270 ml of water were added and the mixture was stirred for 2 hours, then the solution was acidified with hydrochloric acid and the resulting precipitate was filtered off with suction. The solid was washed with water and dried.
수율: 3-티오-2-메틸벤조산 110 g (이론치의 100 %); 융점 155 ℃; 1H-NMR (δ6-DMSO):δ[ppm] = 13.0 (1H, bs), 7.7 (2H, m), 7.3 (1H, tr), 2.4 (3H, s).Yield: 110 g of 3-thio-2-methylbenzoic acid (100% of theory); Melting point 155 ° C .; 1 H-NMR (δ 6 -DMSO): δ [ppm] = 13.0 (1H, bs), 7.7 (2H, m), 7.3 (1H, tr), 2.4 (3H, s).
2. 메틸 3-티오-2-메틸벤조에이트 2. Methyl 3-thio-2-methylbenzoate
3-아미노-2-메틸벤조산 110 g (0.66 몰)을 5 % 황산을 함유하는 메탄올 1.6 l 중에 용해시키고, 그 혼합물을 5 시간 동안 환류하였다. 그 후, 알코올을 증류 제거하고, 잔사를 에틸 아세테이트에 용해시키고, 유기상을 물 및 탄산나트륨으로 세척한 후, 황산나트륨을 사용하여 건조하고 농축시켰다. 110 g (0.66 mol) of 3-amino-2-methylbenzoic acid were dissolved in 1.6 l of methanol containing 5% sulfuric acid and the mixture was refluxed for 5 hours. Thereafter, the alcohol was distilled off, the residue was dissolved in ethyl acetate, and the organic phase was washed with water and sodium carbonate, then dried over sodium sulfate and concentrated.
수율: 메틸 3-티오-2-메틸벤조에이트 104 g (이론치의 87 %); 1H-NMR(CDCl3): δ[ppm] = 7.6 (1H, d), 7.4 (1H, d), 7.1 (1H, d), 3.9 (3H, s), 3.4 (1H, s), 2.5 (3H, s).Yield: 104 g of methyl 3-thio-2-methylbenzoate (87% of theory); 1 H-NMR (CDCl 3 ): δ [ppm] = 7.6 (1H, d), 7.4 (1H, d), 7.1 (1H, d), 3.9 (3H, s), 3.4 (1H, s), 2.5 (3H, s).
3. 메틸 3-티오(2'-프로피온산)-2-메틸벤조에이트 3. Methyl 3-thio (2'-propionic acid) -2-methylbenzoate
메틸 3-티오-2-메틸벤조에이트 70 g (0.38 몰)을 물 400 ml 중에 용해시키고 수산화나트륨 용액 30.8 g (0.77 몰) 및 브로모프로피온산 58.8 g (0.45 몰)과 함께 7 시간 동안 환류시켰다. 냉각 후, 수상을 메틸 tert-부틸 에테르로 세척하였다. 그 후, 수상을 2 N 염산으로 산성화시킨 후, 생성되는 침전물을 흡입으로 여과하고 물로 세척하였고, 그 생성물을 건조시켰다. 70 g (0.38 mol) of methyl 3-thio-2-methylbenzoate were dissolved in 400 ml of water and refluxed with 30.8 g (0.77 mol) of sodium hydroxide solution and 58.8 g (0.45 mol) of bromopropionic acid for 7 hours. After cooling, the aqueous phase was washed with methyl tert-butyl ether. The aqueous phase was then acidified with 2N hydrochloric acid, and the resulting precipitate was filtered off with suction and washed with water and the product dried.
수율: 메틸 3-티오프로피온산-2-메틸벤조에이트 75.5 g (이론치의 78 %);1H-NMR(CDCl3): δ[ppm] = 7.66 (1H, d), 7.51 (1H, d), 7.20 (1H, tr), 3.96 (3H, s), 3.18 (2H, tr), 2.70 (2H, tr), 2.63 (3H, s).Yield: 75.5 g of methyl 3-thiopropionic acid-2-methylbenzoate (78% of theory); 1 H-NMR (CDCl 3 ): δ [ppm] = 7.66 (1H, d), 7.51 (1H, d), 7.20 (1H, tr), 3.96 (3H, s), 3.18 (2H, tr), 2.70 (2H, tr), 2.63 (3H, s).
4. 메틸 8-메틸티오크로만-4-온-7-카르복실레이트4. Methyl 8-methylthiochroman-4-one-7-carboxylate
메틸 3-티오프로피온산-2-메틸벤조에이트 4 g (15.8 밀리몰)을 다중인산 40 g 중에서 70 ℃에서 15 분 동안 교반시켰다. 그 후, 반응 용액을 얼음물에 가하고 생성되는 침전물을 흡입 여과하였다. 생성물을 물로 세척하고 건조실에서 건조시켰다. 고리화 반응의 부산물로서, 메틸 8-메틸티오크로멘-4-온-7-카르복실레이트를 생성하며, 이는 크로마토그래피로 분리할 수 있었다. 4 g (15.8 mmol) of methyl 3-thiopropionic acid-2-methylbenzoate were stirred in 40 g of polyphosphoric acid at 70 ° C. for 15 minutes. Thereafter, the reaction solution was added to ice water and the resulting precipitate was suction filtered. The product was washed with water and dried in a drying room. As a byproduct of the cyclization reaction, methyl 8-methylthiochromen-4-one-7-carboxylate is produced, which can be separated by chromatography.
수율: 메틸 8-메틸티오크로멘-4-온-7-카르복실레이트 3.1 g (이론치의 83 %); 1H-NMR(CDCl3): δ[ppm] = 8.00 (1H, d), 7.30 (1H, d), 3.94 (3H, s), 3.15 (2H, m), 2.98 (2H, m), 2.50 (3H, s);Yield: 3.1 g of methyl 8-methylthiochromen-4-one-7-carboxylate (83% of theory); 1 H-NMR (CDCl 3 ): δ [ppm] = 8.00 (1H, d), 7.30 (1H, d), 3.94 (3H, s), 3.15 (2H, m), 2.98 (2H, m), 2.50 (3H, s);
제2 성분: 메틸 8-메틸티오크로만-4-온-7-카르복실레이트: 1H-NMR (CDCl3): δ[ppm] = 8.4 (1H, d), 7.9 (1H, d), 7.8 (1H, d), 7.0 (1H, d), 4.0 (3H, s), 2.7 (3H, s).Second component: methyl 8-methylthiochroman-4-one-7-carboxylate: 1 H-NMR (CDCl 3 ): δ [ppm] = 8.4 (1H, d), 7.9 (1H, d), 7.8 (1H, d), 7.0 (1H, d), 4.0 (3H, s), 2.7 (3H, s).
5. 8-메틸티오크로만-4-온-7-카르복실산 5. 8-Methylthiochroman-4-one-7-carboxylic acid
메틸 8-메틸티오크로만-4-온-7-카르복실레이트 41.1 g (0.17 몰)을 환류하에서, 물 및 메탄올의 혼합물 400 ml 중 NaOH 10.3 g (0.26 몰)과 함께 가수 분해하였다. 그 후, 메탄올을 증류 제거하고, 잔사를 물로 희석하고, 2 N 염산으로 산성화시켰다. 유용한 생성물을 침전시키고 흡입 여과한 후, 물로 세척하고 건조시켰다. 41.1 g (0.17 mol) of methyl 8-methylthiochroman-4-one-7-carboxylate were hydrolyzed under reflux with 10.3 g (0.26 mol) of NaOH in 400 ml of a mixture of water and methanol. Thereafter, methanol was distilled off and the residue was diluted with water and acidified with 2N hydrochloric acid. The useful product precipitated out, filtered off with suction, washed with water and dried.
수율: 8-메틸티오크로만-4-온-7-카르복실산 34.4 g (이론치의 89 %); 융점 : 243 내지 246 ℃.Yield: 34.4 g of 8-methylthiochroman-4-one-7-carboxylic acid (89% of theory); Melting point: 243 to 246 ° C.
6. 8-메틸-1,1-디옥소티오크로만-4-온-7-카르복실산 6. 8-Methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid
8-메틸티오크로만-4-온-7-카르복실산 20 g (0.09 몰)을 아세트산 100 ml 중에 용해시켰다. 텅스텐산 나트륨을 소량 가하였다. 그 후, 30 % 농도 과산화수소 용액 24.9 g (0.22 몰)을 50 ℃에서 적가하였다. 이어서, 그 혼합물을 약 20 ℃에서 1 시간 동안 교반하였다. 그리고나서, 반응 용액을 물에 가하고, 침전물은 흡입 여과시켰다. 생성물을 물로 세척한 후, 건조시켰다. 20 g (0.09 mol) of 8-methylthiochroman-4-one-7-carboxylic acid was dissolved in 100 ml of acetic acid. A small amount of sodium tungstate was added. Thereafter, 24.9 g (0.22 mol) of a 30% strength hydrogen peroxide solution was added dropwise at 50 ° C. The mixture was then stirred at about 20 ° C for 1 hour. Then the reaction solution was added to water and the precipitate was suction filtered. The product was washed with water and then dried.
수율: 8-메틸-1,1-디옥소티오크로만-4-온-7-카르복실산 18.4 g (이론치의 80 %);융점 : 224 내지 내지 225 ℃.Yield: 18.4 g of 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid (80% of theory); melting point: 224 to 225 ° C.
7. 메틸 4-히드록시-8-메틸티오크로만-7-카르복실레이트 7. Methyl 4-hydroxy-8-methylthiochroman-7-carboxylate
메틸-8-메틸티오크로만-4-온-7-카르복실레이트 30 g (0.127 몰)을 염화메틸렌 120 ml 및 메탄올 60 ml의 혼합물 중에 용해시키고, 0 내지 5 ℃로 냉각시켰다. 그 후, 소듐 보로히드리드 2.4 g (0.064 몰)을 한꺼번에 가하였다. 이어서, 혼합물을 이 온도에서 1 시간 동안 교반하고, 2 N 염산 200 ml를 반응 용액에 가하였다. 두 개의 상이 생성되었다. 유기상은 분리하여 건조시키고, 용매는 증류에 의해서 제거하였다. 조생성물을 추가 정제없이 직접 반응시켰다. 30 g (0.127 mol) of methyl-8-methylthiochroman-4-one-7-carboxylate were dissolved in a mixture of 120 ml of methylene chloride and 60 ml of methanol and cooled to 0-5 ° C. Thereafter, 2.4 g (0.064 mol) of sodium borohydride were added all at once. The mixture was then stirred at this temperature for 1 hour and 200 ml of 2N hydrochloric acid was added to the reaction solution. Two phases were created. The organic phase was separated and dried and the solvent was removed by distillation. The crude product was reacted directly without further purification.
수율: 메틸 4-히드록시-8-메틸티오크로만-7-카르복실레이트 27.6 g (이론치의 91 %).Yield: 27.6 g of methyl 4-hydroxy-8-methylthiochroman-7-carboxylate (91% of theory).
8. 메틸 4-에톡시-8-메틸티오크로만-7-카르복실레이트 8. Methyl 4-ethoxy-8-methylthiochroman-7-carboxylate
메틸-4-히드록시-8-메틸티오크로만-7-카르복실레이트 13.8 g (0.058 몰)을 황산 1 g을 첨가하여 에탄올 60 ml 중에서 4 시간 동안 비점에서 가열하였다. 그 후, 용매를 증류 제거하고 잔사를 물에 용해시켰다. 수상을 에틸 아세테이트로 추출하였다. 유기상을 탄산수소나트륨 용액으로 세척하고, 건조시켜 농축하였다. 생성물을 크로마토그래피로 정제하였다. 13.8 g (0.058 mol) of methyl-4-hydroxy-8-methylthiochroman-7-carboxylate were heated at boiling point in 60 ml of ethanol for 4 hours with the addition of 1 g of sulfuric acid. Thereafter, the solvent was distilled off and the residue was dissolved in water. The aqueous phase was extracted with ethyl acetate. The organic phase was washed with sodium hydrogen carbonate solution, dried and concentrated. The product was purified by chromatography.
수율: 메틸 4-에톡시-8-메틸티오크로만-7-카르복실레이트 10.1 g (이론치의 60 %);1H-NMR(CDCl3): δ[ppm] = 7.44 (1H, d), 7.13 (1H, d), 4.40 (1H, m), 3.90 (3H, s), 3.60 (2H, m), 3.38 (1H, dtr), 2.90 (1H, m), 2.50 (3H, s), 2.40 (1H, m), 1.98 (1H, m), 1.10 (3H, tr).Yield: 10.1 g of methyl 4-ethoxy-8-methylthiochroman-7-carboxylate (60% of theory); 1 H-NMR (CDCl 3 ): δ [ppm] = 7.44 (1H, d), 7.13 (1H, d), 4.40 (1H, m), 3.90 (3H, s), 3.60 (2H, m), 3.38 (1H, dtr), 2.90 (1H, m), 2.50 (3H, s), 2.40 (1H, m), 1.98 (1H, m), 1.10 (3H, tr).
메틸 4-메톡시-8-메틸티오크로만-4-온-7-카르복실레이트 및 메틸 4-이소프로폭시-8-메틸티오크로만-4-온-7-카르복실레이트를 생성하는 반응은 상기 방법과 유사하게 수행되며, 메틸 4-메톡시-8-메틸티오크로만-4-온-7-카르복실레이트의 경우에 에탄올이 메탄올로 대체되고, 메틸 4-이소프로폭시-8-메틸티오크로만-4-온-7-카르복실레이트의 경우, 에탄올이 이소프로판올로 대체되었다. Reaction to produce methyl 4-methoxy-8-methylthiochroman-4-one-7-carboxylate and methyl 4-isopropoxy-8-methylthiochroman-4-one-7-carboxylate Is carried out analogously to the above process, in the case of methyl 4-methoxy-8-methylthiochroman-4-one-7-carboxylate, ethanol is replaced by methanol and methyl 4-isopropoxy-8- For methylthiochroman-4-one-7-carboxylate, ethanol was replaced with isopropanol.
9. 4-에톡시-8-메틸티오크로만-7-카르복실산 9. 4-ethoxy-8-methylthiochroman-7-carboxylic acid
수산화나트륨 용액 2.1 g을 물 20 ml 중에 용해시켰다. 메탄올 20 ml 중에 용해된 메틸 4-에톡시-8-메틸티오크로만-4-온-7-카르복실레이트를 약 20 ℃에서 적가하였다. 그 혼합물을 2 시간 동안 환류시켰다. 그 후, 용매를 증류 제거하고, 잔사를 2 N 염산에 가하였다. 수상을 염화메틸렌으로 추출하고, 유기상을 건조 농축하였다. 2.1 g of sodium hydroxide solution was dissolved in 20 ml of water. Methyl 4-ethoxy-8-methylthiochroman-4-one-7-carboxylate dissolved in 20 ml of methanol was added dropwise at about 20 ° C. The mixture was refluxed for 2 hours. Thereafter, the solvent was distilled off and the residue was added to 2N hydrochloric acid. The aqueous phase was extracted with methylene chloride and the organic phase was concentrated to dryness.
수율: 4-에톡시-8-메틸티오크로만-7-카르복실산 9.3 g (이론치의 100 %);융점 : 89 내지 98 ℃.Yield: 9.3 g of 4-ethoxy-8-methylthiochroman-7-carboxylic acid (100% of theory); Melting point: 89 to 98 ° C.
4-에톡시-8-메틸티오크로만-7-카르복실산 및 4-이소프로폭시-8-메틸티오크로만-7-카르복실산에 상응하는 에스테르의 가수분해는 유사한 방법으로 수행된다. 동일한 방법을 사용하여, 하기 나타낸 상응하는 벤조[b]티오펜 유도체의 가수분해를 수행한다. Hydrolysis of the esters corresponding to 4-ethoxy-8-methylthiochroman-7-carboxylic acid and 4-isopropoxy-8-methylthiochroman-7-carboxylic acid is carried out in a similar manner. Using the same method, hydrolysis of the corresponding benzo [b] thiophene derivatives shown below is carried out.
10. 8-메틸-4-에톡시-1,1-디옥소티오크로만-7-카르복실산 10. 8-Methyl-4-ethoxy-1,1-dioxothiochroman-7-carboxylic acid
4-에톡시-8-메틸티오크로만-7-카르복실산 8.4 g (0.033 몰)을 아세트산 60 ml 중에 먼저 투입하였다. 텅스텐산 나트륨을 소량 가하였다. 그 후, 30 % 농도 과산화수소 용액 7.9 g (0.07 몰)을 50 ℃에서 적가하고, 이어 반응 혼합물을 2 시간 동안 교반하였다. 그리고나서, 반응 용액을 물에 붓고 수상을 에틸아세테이트로 추출하였다. 유기상을 중아황산염 용액으로 세척하고, 건조 농축하였다. 8.4 g (0.033 mol) of 4-ethoxy-8-methylthiochroman-7-carboxylic acid was first charged in 60 ml of acetic acid. A small amount of sodium tungstate was added. Thereafter, 7.9 g (0.07 mol) of a 30% strength hydrogen peroxide solution was added dropwise at 50 ° C, and the reaction mixture was then stirred for 2 hours. Then, the reaction solution was poured into water and the aqueous phase was extracted with ethyl acetate. The organic phase was washed with bisulfite solution and concentrated to dryness.
수율: 8-메틸-4-에톡시-1,1-디옥소티오크로만-7-카르복실산 9.5 g (이론치의 100 %); 융점 : 150 ℃. Yield: 9.5 g of 8-methyl-4-ethoxy-1,1-dioxothiochroman-7-carboxylic acid (100% of theory); Melting point: 150 ° C.
11. 8-메틸티오크로만-4-온-7-카르복실산 O-에틸 옥심 11. 8-methylthiochroman-4-one-7-carboxylic acid O-ethyl oxime
에틸히드록시아민 0.88 g (9 밀리몰)을 20 ml의 메탄올 중에 먼저 투입하였다. 탄산칼륨 0.62 g (4.5 밀리몰)을 가하고나서, 8-메틸티오크로만-4-온-7-카르복실산 2.0 g (9 밀리몰)을 가하였다. 반응물을 약 20 ℃에서 10 일 동안 교반하였다. 물 및 2 N 염산을 가함으로써 마무리 처리하고, 생성되는 침전물을 흡입 여과하고 건조하였다. 0.88 g (9 mmol) of ethylhydroxyamine was first charged in 20 ml of methanol. 0.62 g (4.5 mmol) of potassium carbonate was added followed by 2.0 g (9 mmol) of 8-methylthiochroman-4-one-7-carboxylic acid. The reaction was stirred at about 20 ° C for 10 days. Finished by addition of water and 2N hydrochloric acid, and the resulting precipitate was suction filtered and dried.
수율: 8-메틸티오크로만-4-온-7-카르복실산 O-에틸 옥심 2.2 g (이론치의 92 %); 융점 : 166 ℃.Yield: 2.2 g of 8-methylthiochroman-4-one-7-carboxylic acid O-ethyl oxime (92% of theory); Melting point: 166 캜.
12. 8-메틸-1,1-디옥소티오크로만-4-온-7-카르복실산 O-에틸 옥심12. 8-Methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid O-ethyl oxime
8-메틸티오크로만-4-온-7-카르복실산 O-에틸 옥심 3.0 g (0.011 몰)을 아세트산 30 ml 중에 텅스텐산나트륨 소량과 함께 투입하였다. 그 후, 30 % 농도 과산화수소 용액 2.8 g (0.024 몰)을 50 ℃에서 적가하였다. 1 시간 동안 교반한 후, 반응 혼합물을 얼음물에 붓고, 생성되는 침전물은 흡입 여과하였다. 생성물을 물로 세척한 후, 건조시켰다. 3.0 g (0.011 mol) of 8-methylthiochroman-4-one-7-carboxylic acid O-ethyl oxime was charged with a small amount of sodium tungstate in 30 ml of acetic acid. Thereafter, 2.8 g (0.024 mol) of a 30% strength hydrogen peroxide solution was added dropwise at 50 ° C. After stirring for 1 hour, the reaction mixture was poured into ice water and the resulting precipitate was suction filtered. The product was washed with water and then dried.
수율: 8-메틸-1,1-디옥소티오크로만-4-온-7-카르복실산 O-에틸 옥심 2.5 g (이론치의 74 %); 융점 198 ℃.Yield: 2.5 g of 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid O-ethyl oxime (74% of theory); Melting point 198 ° C.
13. 8-메틸-1-옥소티오크로만-4-온-7-카르복실산 13. 8-Methyl-1-oxothiochroman-4-one-7-carboxylic acid
8-메틸티오크로만-4-온-7-카르복실산 7.0 g (31.5 밀리몰)을 아세트산 70 ml 중에 텅스텐산나트륨 소량과 함께 투입하였다. 30 % 농도 과산화 수소 용액 3.6 g (31.5 밀리몰)을 50 ℃에서 적가하고 나서, 반응 용액을 3 시간 동안 교반하였다. 그 후, 물 중에서 교반하고, 생성물을 에틸 아세테이트로 추출하였다. 유기상을 건조하고 용매를 제거하였다. 생성물을 크로마토그래피로 정제하였다. 7.0 g (31.5 mmol) of 8-methylthiochroman-4-one-7-carboxylic acid were charged with a small amount of sodium tungstate in 70 ml of acetic acid. 3.6 g (31.5 mmol) of 30% strength hydrogen peroxide solution were added dropwise at 50 ° C, and the reaction solution was stirred for 3 hours. Then it was stirred in water and the product was extracted with ethyl acetate. The organic phase was dried and the solvent removed. The product was purified by chromatography.
수율: 8-메틸-1-옥소티오크로만-4-온-7-카르복실산 5.4 g (이론치의 72 %); 1H-NMR(δ6-DMSO):δ[ppm] = 8.0 (2H, m), 3.5 (3H, m), 2.8 (1H, m), 2.7 (3H, s).Yield: 5.4 g of 8-methyl-1-oxothiochroman-4-one-7-carboxylic acid (72% of theory); 1 H-NMR (δ 6 -DMSO): δ [ppm] = 8.0 (2H, m), 3.5 (3H, m), 2.8 (1H, m), 2.7 (3H, s).
14. 메틸 3-카르복시메틸티오-2-메틸벤조에이트 14. Methyl 3-carboxymethylthio-2-methylbenzoate
디메틸포름아미드 80 ml 중의 메틸-3-메르캅토-2-메틸벤조에이트 12.4 g (0.068 밀리몰)을 디메틸포름아미드 40 ml 중의 수소화나트륨 1.6 g (0.068 몰)에 적가하고, 그 혼합물을 약 20 ℃에서 60 분간 교반하였다. 그 후, 클로로아세트산 8 g (0.068몰)을 가한 후, 혼합물을 약 20 ℃에서 4 시간 동안 교반하였다. 12.4 g (0.068 mmol) of methyl-3-mercapto-2-methylbenzoate in 80 ml of dimethylformamide are added dropwise to 1.6 g (0.068 mol) of sodium hydride in 40 ml of dimethylformamide and the mixture is added at about 20 ° C. Stir for 60 minutes. Thereafter, 8 g (0.068 mol) of chloroacetic acid was added, and the mixture was stirred at about 20 ° C. for 4 hours.
반응 혼합물을 염산을 함유하는 얼음물에 넣어 교반함으로써 마무리 처리하였다. The reaction mixture was finished by pouring into iced water containing hydrochloric acid and stirring.
생성되는 침전물을 흡입 여과하고, 물로 세척, 건조하였다. The resulting precipitate was suction filtered, washed with water and dried.
수율: 메틸-3-카르복시메틸티오-2-메틸벤조에이트 14.6 g (이론치의 89 %);1H-NMR (δ6-DMSO):δ[ppm] = 7.55 (1H, d), 7.45 (1H, d), 7.21 (1H, tr), 3.82 (2H, s), 2.5 (3H, s).Yield: 14.6 g of methyl-3-carboxymethylthio-2-methylbenzoate (89% of theory); 1 H-NMR (δ 6 -DMSO): δ [ppm] = 7.55 (1H, d), 7.45 (1H, d), 7.21 (1H, tr), 3.82 (2H, s), 2.5 (3H, s) .
15. 메틸 7-메틸벤조[b]티오펜-3[2H]-온-6-카르복실레이트 15. Methyl 7-methylbenzo [b] thiophene-3 [2H] -one-6-carboxylate
3-카르복시메틸티오-2-메틸벤조산 14.3 g (0.06 밀리몰)을 염화메틸렌 300 ml 중에 용해시키고, 티오닐 클로라이드 13.1 g (0.11 밀리몰)을 적가하였다. 혼합물을 1 시간 동안 환류시키고 나서, 용매 및 과량의 티오닐 클로라이드를 증류 제거시켰다. 잔사를 염화메틸렌 100 ml 중에 용해시키고, 삼염화 알루미늄 31.8 g (0.24 밀리몰)로 처리하였다. 반응물을 약 20 ℃에서 1 시간 동안 교반하였다. 그 후, 혼합물을 얼음물에 가하고 유기상을 분리하였다. 유기상을 세척하고 건조시킨 후, 용매를 제거하였다 생성물을 정제없이 추가 반응시켰다.14.3 g (0.06 mmol) of 3-carboxymethylthio-2-methylbenzoic acid were dissolved in 300 ml of methylene chloride and 13.1 g (0.11 mmol) of thionyl chloride was added dropwise. The mixture was refluxed for 1 hour, and then the solvent and excess thionyl chloride were distilled off. The residue was dissolved in 100 ml of methylene chloride and treated with 31.8 g (0.24 mmol) of aluminum trichloride. The reaction was stirred at about 20 ° C for 1 hour. Then the mixture was added to ice water and the organic phase was separated. After the organic phase was washed and dried, the solvent was removed. The product was further reacted without purification.
수율: 메틸 7-메틸벤조[b]-티오펜-3[2H]-온-6-카르복실레이트 12.9 g (이론치의 97 %); 1H-NMR (CDCl3)):δ[ppm] = 7.65 (2H, m), 3.93 (3H, s), 3.88 (2H, s), 2.50 (3H, s).Yield: 12.9 g of methyl 7-methylbenzo [b] -thiophen-3 [2H] -one-6-carboxylate (97% of theory); 1 H-NMR (CDCl 3 )): δ [ppm] = 7.65 (2H, m), 3.93 (3H, s), 3.88 (2H, s), 2.50 (3H, s).
16. 메틸 7-메틸-3-히드록시벤조[b]티오펜-[2H]-6-카르복실레이트16. Methyl 7-methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylate
메틸 7-메틸벤조[b]티오펜-3[2H]-온-6-카르복실레이트 12.8 g (0.058 몰)을 염화메틸렌 120 ml 및 메탄올 60 ml 중에 용해시키고 0 ℃로 냉각시켰다. 소듐 보로히드리드 1.1 g (0.029 몰)을 한꺼번에 가하고, 그 혼합물을 3 시간 동안 교반하였다. 물을 가함으로써 반응을 종결하였다. 상을 분리하여 수상을 염화메틸렌으로 추출하였다. 합한 유기상을 건조시키고 용매를 증류 제거하였다. 조생성물을 추가 반응시켰다. 12.8 g (0.058 mol) of methyl 7-methylbenzo [b] thiophene-3 [2H] -one-6-carboxylate was dissolved in 120 ml of methylene chloride and 60 ml of methanol and cooled to 0 ° C. 1.1 g (0.029 mol) of sodium borohydride were added all at once and the mixture was stirred for 3 hours. The reaction was terminated by adding water. The phases were separated and the aqueous phase was extracted with methylene chloride. The combined organic phases were dried and the solvent was distilled off. The crude product was further reacted.
수율: 메틸 7-메틸-3-히드록시벤조[b]-티오펜-[2H]-6-카르복실레이트 13.2 g (이론치의 100 %); 1H-NMR (CDCl3)):δ[ppm] = 7.6 (2H, m), 5.3 (1H, m), 3.9 (3H, s), 3.7 (1H, m), 3.3 (1H, m), 2.4 (3H, s).Yield: 13.2 g of methyl 7-methyl-3-hydroxybenzo [b] -thiophene- [2H] -6-carboxylate (100% of theory); 1 H-NMR (CDCl 3 )): δ [ppm] = 7.6 (2H, m), 5.3 (1H, m), 3.9 (3H, s), 3.7 (1H, m), 3.3 (1H, m), 2.4 (3H, s).
17. 메틸 7-메틸-3-히드록시벤조[b]티오펜-[2H]-6-카르복실레이트 17. Methyl 7-methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylate
NaH 2.4 g (0.059 몰)을 50 mL의 디메틸 포름아미드 중에 용해하였다. 50 mL의 디메틸 포름아미드 중의 메틸 7-메틸-3-히드록시벤조[b]티오펜-[2H]-6-카르복실레이트 13.2 g을 적가하고, 그 혼합물을 20 ℃에서 2 시간 동안 교반시켰다. 그 후, 요오도메탄 8.4 g (0.059 몰)을 가하고, 그 혼합물을 2 시간 동안 추가로 교반하였다. 반응 용액을 얼음물에 가하고, 에틸 아세테이트로 추출하였다. 유기상을 건조, 농축시키고, 생성물을 크로마토그래피로 정제하였다. 2.4 g (0.059 mol) of NaH were dissolved in 50 mL of dimethyl formamide. 13.2 g of methyl 7-methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylate in 50 mL of dimethyl formamide was added dropwise and the mixture was stirred at 20 ° C. for 2 hours. Then 8.4 g (0.059 mol) of iodomethane were added and the mixture was further stirred for 2 hours. The reaction solution was added to ice water and extracted with ethyl acetate. The organic phase is dried, concentrated and the product is purified by chromatography.
수율: 메틸 7-메틸-3-히드록시벤조[b]티오펜-[2H]-6-카르복실레이트 3.5 g (이론치의 25 %); 1H-NMR (CDCl3):δ[ppm] = 7.60 (1H, d), 7.20 (1H, d), 5.04 (1H, m), 3.90 (3H, s), 3.56 (1H, m), 3.40 (3H, s), 3.38 (1H, m), 2.50 (3H, s).Yield: 3.5 g of methyl 7-methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylate (25% of theory); 1 H-NMR (CDCl 3 ): δ [ppm] = 7.60 (1H, d), 7.20 (1H, d), 5.04 (1H, m), 3.90 (3H, s), 3.56 (1H, m), 3.40 (3H, s), 3.38 (1H, m), 2.50 (3H, s).
또한, 상기 설명한 티오크로마논 에스테르의 가수분해와 유사하게, 상응하는 벤조티오펜산을 얻을 수 있다. In addition, similar to the hydrolysis of the thiochromenone esters described above, the corresponding benzothiophenic acid can be obtained.
하기 표에서 나타낸 화합물은 유사한 방법으로 얻어진다.The compounds shown in the table below are obtained in a similar manner.
<표 12aa>TABLE 12aa
중간체Intermediate
<표 12ab>TABLE 12ab
<표 12ac>Table 12ac
<표 12a>TABLE 12a
중간체Intermediate
<최종 생성물의 제조>Preparation of Final Product
1. 2-(8-메틸-1,1-디옥소티오크로만-4-온-7-카르보닐)-1,3-시클로헥산디온1.2- (8-Methyl-1,1-dioxothiochroman-4-one-7-carbonyl) -1,3-cyclohexanedione
a) 8-메틸-1,1-디옥소티오크로만-4-온-7-카르복실산 17.4 g (0.0685 몰)을 톨루엔 170 ml중에 용해시키고, 디메틸포름아미드 한 방울로 처리한 후, 티오닐 클로라이드 8.96 g (0.0753 몰)을 가하였다. 4 시간 동안 환류시킨 후, 반응 혼합물을 농축시켰다. 반응 생성물을 직접 추가 반응시켰다. a) 17.4 g (0.0685 mol) of 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid is dissolved in 170 ml of toluene and treated with a drop of dimethylformamide, followed by 8.96 g (0.0753 mol) of onyl chloride were added. After refluxing for 4 hours, the reaction mixture was concentrated. The reaction product was further reacted directly.
수율: 8-메틸-1,1-디옥소티오크로만-4-온-7-카르보닐 클로라이드 18.6 g (이론치의 99%)Yield: 18.6 g of 8-methyl-1,1-dioxothiochroman-4-one-7-carbonyl chloride (99% of theory)
b) 시클로헥산-1,3-디온 0.62 g (5.5 밀리몰)을 트리에틸아민 0.56 g (5.5 몰)과 함께 아세토니트릴 10 ml 중으로 먼저 투입하였다. 아세토니트릴 20 ml 중의 8-메틸-1,1-디옥소티오크로만-4-온-7-카르보닐 클로라이드를 적가하였다. b) 0.62 g (5.5 mmol) of cyclohexane-1,3-dione were first introduced into 10 ml of acetonitrile together with 0.56 g (5.5 mol) of triethylamine. 8-methyl-1,1-dioxothiochroman-4-one-7-carbonyl chloride in 20 ml of acetonitrile was added dropwise.
후속해서, 혼합물을 약 2 ℃에서 1 시간 동안 교반하였다. 그 후, 아세톤 시아노히드린 0.31 g (3.7 밀리몰) 및 트리에틸아민 2.8 g (22.5 밀리몰)을 가하고, 그 혼합물을 1 시간 동안 교반하였다. 마무리 처리를 위해서 반응 용액을 2 N 염산 중에서 교반하고, 유기상을 에틸 아세테이트로 추출하였다. 그 후, 유기상을 Na2CO3용액으로 추출하고, 알칼리 수상을 냉각시키면서 산성화하였다. 생성되는 침전물을 흡입 여과하고, 물로 세척하고 건조시켰다.Subsequently, the mixture was stirred at about 2 ° C for 1 hour. Then 0.31 g (3.7 mmol) acetone cyanohydrin and 2.8 g (22.5 mmol) triethylamine were added and the mixture was stirred for 1 hour. The reaction solution was stirred in 2N hydrochloric acid for finishing treatment and the organic phase was extracted with ethyl acetate. The organic phase was then extracted with Na 2 CO 3 solution and acidified while cooling the alkaline aqueous phase. The resulting precipitate was suction filtered, washed with water and dried.
수율: 2-(8-메틸-1,1-디옥소티오크로만-4-온-7-카르보닐)-1,3-시클로헥산디온 1.0 g (이론치의 52 %); 융점 173 내지 178 ℃Yield: 1.0 g of 2- (8-methyl-1,1-dioxothiochroman-4-one-7-carbonyl) -1,3-cyclohexanedione (52% of theory); Melting Point 173-178 ° C
2. 2-(8-메틸-1,1-디옥소티오크로만-4-온-7-카르보닐 O-에틸 옥심)시클로헥산-1,3 -디온2. 2- (8-Methyl-1,1-dioxothiochroman-4-one-7-carbonyl O-ethyl oxime) cyclohexane-1,3-dione
8-메틸-1,1-디옥소크로만-4-온-7-카르복실산 O-에틸 옥심 1.0 g (3.4 밀리몰)을 시클로헥산-1,3-디온 0.39 g (3.5 밀리몰)과 함께 아세토니트릴 10 ml 중에 먼저 투입하였다. 디시클로카르보디이미드 (DCC) 0.75 g (3.6 밀리몰)을 가하고, 그 혼합물을 2 시간 동안 교반하였다. 그리고 나서, 아세톤 시아노히드린 0.1 ml 및 트리에틸아민 0.51 g (5.1 밀리몰)을 가하고, 그 반응 혼합물을 2 시간 동안 추가로 교반하였다. 그 후, 탄산나트륨 용액 중에서 교반하고, 에틸 아세테이트로 추출한 후, 유기상을 제거하였다. 수상을 염산을 사용하여 산성화하고 에틸 아세테이트로 다시 추출한 후, 유기상을 건조하고, 용매를 증류 제거하였다. 생성물을 크로마토그래피로 정제하였다. 1.0 g (3.4 mmol) of 8-methyl-1,1-dioxochroman-4-one-7-carboxylic acid O-ethyl oxime with aceto with 0.39 g (3.5 mmol) of cyclohexane-1,3-dione First in 10 ml nitrile. 0.75 g (3.6 mmol) of dicyclocarbodiimide (DCC) was added and the mixture was stirred for 2 hours. 0.1 ml of acetone cyanohydrin and 0.51 g (5.1 mmol) of triethylamine were then added and the reaction mixture was further stirred for 2 hours. Thereafter, the mixture was stirred in sodium carbonate solution, extracted with ethyl acetate, and the organic phase was removed. The aqueous phase was acidified with hydrochloric acid and extracted again with ethyl acetate, then the organic phase was dried and the solvent was distilled off. The product was purified by chromatography.
수율: 2-(8-메틸-1,1-디옥소티오크로만-4-온-7-카르보닐 O-에틸 옥심)시클로헥산-1,3-디온 600 mg (이론치의 45 %); 융점: 143 ℃.Yield: 600 mg of 2- (8-methyl-1,1-dioxothiochroman-4-one-7-carbonyl O-ethyl oxime) cyclohexane-1,3-dione (45% of theory); Melting point: 143 ° C.
3. 2-(8-메틸-4-에톡시-1,1-디옥소티오크로만-7-카르보닐)시클로헥산-1,3-디온3. 2- (8-Methyl-4-ethoxy-1,1-dioxothiochroman-7-carbonyl) cyclohexane-1,3-dione
a) 8-메틸-4-에톡시-1,1-디옥소티오크로만-7-카르복실산 8.8 g (0.031 밀리몰)을 톨루엔 50 ml 중에 용해시키고, 그 용액을 디메틸포름아미드 2 방울로 처리한 후, 티오닐 클로라이드 4.4 g (0.04 밀리몰)을 가하였다. 4 시간 동안 환류시킨 후, 반응 혼합물을 농축시켰다. 산 클로라이드를 직접 추가 사용하였다. a) 8.8 g (0.031 mmol) of 8-methyl-4-ethoxy-1,1-dioxothiochroman-7-carboxylic acid is dissolved in 50 ml of toluene and the solution is treated with 2 drops of dimethylformamide. Then, 4.4 g (0.04 mmol) thionyl chloride was added. After refluxing for 4 hours, the reaction mixture was concentrated. Acid chloride was further used directly.
b) 시클로헥산-1,3-디온 0.56 g을 피리딘 0.47 g (6 밀리몰)과 함께 염화메틸렌 10 ml 중으로 먼저 투입하였다. 염화메틸렌 20 ml 중 3a)으로부터의 산 클로라이드 1.5 g (5 밀리몰)을 적가하고 나서, 그 혼합물을 1 시간 동안 교반하였다. 반응 용액을 물에 가하고, 염산으로 산성화하였다. 수상을 에틸 아세테이트로 추출하고, 유기상을 건조시킨 후, 용매를 제거하였다. b) 0.56 g of cyclohexane-1,3-dione was first introduced into 10 ml of methylene chloride together with 0.47 g (6 mmol) of pyridine. 1.5 g (5 mmol) of acid chloride from 3a) in 20 ml of methylene chloride were added dropwise and the mixture was stirred for 1 hour. The reaction solution was added to water and acidified with hydrochloric acid. The aqueous phase was extracted with ethyl acetate and the organic phase was dried and then the solvent was removed.
수율: O-아실화된 생성물 1.88 g (이론치의 99 %).Yield: 1.88 g of O-acylated product (99% of theory).
c) 3b)로부터의 생성물 1.3 g (3.4 밀리몰)을 아세토니트릴 20 ml 중에 용해시켰다. 그 후, 반응 혼합물을 아세톤 시아노히드린 0.19 g (2.3 밀리몰) 및 트리에틸아민 1.7 g (17.2 밀리몰)을 가하고, 그 혼합물을 2 시간 동안 교반하였다. 2N 염산을 가하고, 에틸 아세테이트로 추출하였다. 유기상을 탄산나트륨으로 세척하여 제거하였다. 마지막으로, 알칼리 수상을 염산으로 산성화하였다. 생성되는 침전물을 흡입 여과하고 건조하였다. c) 1.3 g (3.4 mmol) of the product from 3b) were dissolved in 20 ml of acetonitrile. Thereafter, 0.19 g (2.3 mmol) of acetone cyanohydrin and 1.7 g (17.2 mmol) of triethylamine were added, and the mixture was stirred for 2 hours. 2N hydrochloric acid was added and extracted with ethyl acetate. The organic phase was removed by washing with sodium carbonate. Finally, the alkaline aqueous phase was acidified with hydrochloric acid. The resulting precipitate was suction filtered and dried.
수율: 2-(8-메틸-4-에톡시-1,1-디옥소티오크로만-7-카르보닐)시클로헥산-1,3-디온 0.6 g (이론치의 46 %); 1H-NMR(CDCl3): δ[ppm] = 17.5 (1H, s), 7.30 (1H, d), 7.18 (1H, d), 4.47 (1H, m), 3.95-3.83 (1H, m), 3.70-3.50 (2H, m), 3.28 (1H, m), 2.81 (2H, tr), 2.71-2.50 (2H, m), 2.64 (3H, s), 2.43 (2H, tr), 2.05 (2H, m), 1.24 (3H, tr).Yield: 0.6 g of 2- (8-methyl-4-ethoxy-1,1-dioxothiochroman-7-carbonyl) cyclohexane-1,3-dione (46% of theory); 1 H-NMR (CDCl 3 ): δ [ppm] = 17.5 (1H, s), 7.30 (1H, d), 7.18 (1H, d), 4.47 (1H, m), 3.95-3.83 (1H, m) , 3.70-3.50 (2H, m), 3.28 (1H, m), 2.81 (2H, tr), 2.71-2.50 (2H, m), 2.64 (3H, s), 2.43 (2H, tr), 2.05 (2H , m), 1.24 (3H, tr).
하기 표에서 나타낸 화합물을 유사한 방법으로 얻었다:The compounds shown in the following table were obtained in a similar manner:
<표 13a>TABLE 13a
하기 화학식의 화합물 Compound of formula
<표 13b>TABLE 13b
<표 13c>TABLE 13c
<표 13d>TABLE 13D
<표 13e>TABLE 13e
<표 14>TABLE 14
하기 화학식의 화합물 Compound of formula
<표 15>TABLE 15
하기 화학식의 화합물 Compound of formula
<표 16>TABLE 16
하기 화학식의 화합물 Compound of formula
화합물 I 및 그의 농업적으로 이용가능한 염은 이성질체 혼합물 및 순수한 이성질체 두 가지 형태로서 제초제에 적합하다. 이성질체 함유 제조제 조성물은 특히 높은 시용율로, 비-농작물 부분에 대한 매우 효과적인 식물 성장 억제를 수행하게 한 다. 그들은 밀, 쌀, 옥수수, 대두 및 목화와 같은 농작물에 크게 해를 주지 않으면서 넓은 잎의 잡초 및 풀잡초를 억제할 수 있다. 이러한 효과는 특히 낮은 시용율에서 뚜렷하다.Compound I and its agriculturally available salts are suitable for herbicides in both isomeric mixtures and pure isomers. Isomer-containing preparation compositions, in particular with high application rates, allow to perform very effective plant growth inhibition on non-crop parts. They can control broad-leaf weeds and grass weeds without significantly harming crops such as wheat, rice, corn, soybeans, and cotton. This effect is especially pronounced at low application rates.
시용 방법의 다양성을 고려하여, 화합물 I 또는 그를 함유하는 조성물은 바람직하지 못한 식물을 제거하기 위한 보다 많은 농작물에 부가적으로 사용될 수 있다. 적합한 농작물의 예로는 알리움 세파 (Allium cepa), 아나나스 코모수스 (Ananas comosus), 아라키스 히포가에아 (Arachis hypogaea), 아스파라거스 오피시날리스 (Asparagus officinalis), 베타 불가리스 종 알티시마 (Beta vulgaris spec. altissima), 베타 불가리스 종 라파 (Beta vulgaris spec. rapa), 브라시카 나푸스 변종 나푸스 (Brassica napus var. napus), 브라시카 나푸스 변종 나포브라시카 (Brassica napus var. napobrassica), 브라시카 라파 변종 실베스트리스 (Brassica rapa var. silvestris), 카멜리아 시넨시스 (Camellia sinensis), 칼타무스 틴크토리우스 (Carthamus tinctorius), 칼야 일리노이넨시스 (Carya illinoinensis), 시트러스 리몬 (Citrus limon), 시트러스 시넨시스 (Citrus sinensis), 코페아 아라비카 (Coffea arabica), (코페아 카네포라 (Coffea canephora), 코페아 리베리카 (Coffea liberica)), 쿠쿠미스 사티버스 (Cucumis sativus), 시노돈 닥틸론 (Cynodon dactylon), 다우커스 카로타 (Daucus carota), 엘아에이스 귀닌시스 (Elaeis guineensis), 프라가리아 베스카 (Fragaria vesca), 글리신 맥스 (Glycine max), 고시피움 힐수텀 (Gossypium hirsutum), ((고시피움 알보레움 (Gossypium arboreum), 고시피움 헐바세움 (Gossypium herbaceum), 고시피움 비티폴리움 (Gossypium vitifolium)), 헬리안터스 안누스 (Helianthus annuus), 헤베아 브라실리엔시스 (Hevea brasiliensis), 홀데움 불가레 (Hordeum vulgare), 후물러스 루펄러스 (Humulus lupulus), 이포모에아 베타타스 (Ipomoea batatas), 저글란스 레지아 (Juglans regia), 렌스 컬리나리스 (lens culinaris), 리넘 우시타티시멈 (Linum usitatissimum), 리코펄시콘 리코펄시컴 (Lycopersicon lycopersicum), 말러스 종 (Malus spec.), 마니홋 에스컬렌타 (Manihot esculenta), 메티카고 사티바 (Medicago sativa), 무사 종 (Musa spec.), 니코티아나 타바컴 (Nicotiana tabacum) (니코티아나 루스티카 (N. rustica)), 올레아 유로파에아 (Olea europaea), 오리자 사티바 (Oryza sativa), 파세올러스 루나터스 (Phaseolus lunatus), 파에올러스 불가리스 (Phaseolus Vulgaris), 피세아 아비에스 (Picea abies), 피너스 종 (Pinus spec.), 피섬 사티범 (Pisum sativum), 프루너스 아미움 (Prunus avium), 프루너스 펄시카 (Prunus persica), 피러스 콤뮤니스 (Pyrus communis), 리베스 실베스트레 (Ribes sylvestre), 리시너스 콤뮤니스 (Ricinus communis), 사카럼 오피시나럼 (Saccharum officinarum), 세칼레 세닐레 (Secale cereale), 솔라넘 튜버로섬 (Solanum tuberosum), 솔스험 비콜러 (Sorghum bicolor (솔스험 불가레 (S. vulgare)), 테오브로마 카카오 (Theobroma cacao), 트리폴리움 프라텐세 (Trifolium pratense), 트리티컴 아에스티범 (Triticum aestivum), 트리티컴 듀럼 (Triticum durum), 비시카 파바 (Vicia faba), 비티스 비니페라 (Vitis vinifera) 및 제아 마이스 (Zea mays)가 있다.In view of the variety of methods of application, compound I or a composition containing it can be used in addition to more crops for removing undesirable plants. Examples of suitable crops include Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris species Altishima altissima), Beta vulgaris spec.rapa, Brassica napus var.napus, Brassica napus var. Napobrasica, Brassica rapa Variant Silvestris (Brassica rapa var.silvestris), Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis sinensis, Copea arabica, (Coffea canephora, Copea liberica), Cucumis sativus, Sino Cynodon dactylon, Dauscus carota, Elaeis guineensis, Fragararia vesca, Glycine max, Gossypium hirsutum , ((Gossypium arboreum), Gossypium herbaceum, Gossypium vitifolium, Helianthus annuus, Hevea brasiliensis (Hevea) brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Meticago sativa, Musa spec., Nicotiana Tabacum, Nicotiana tabacum) (Nicotiana Rustica (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus Vulgaris, Picea abies , Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Lives sylvestre Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solarum tuberosum, Solshum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Visica Vicia faba, Vitis vinifera and Zea mays have.
더우기, 화합물 I은 유전자 기술 방법에 의한 품종 개량의 결과로서 제초제 작용에 내성이 있는 농작물에 사용될 수 있다. Moreover, Compound I can be used in crops that are resistant to herbicide action as a result of breed improvement by genetic engineering methods.
화합물 I 및 그를 함유하는 제초제 조성물은 예를 들어, 즉시 사용가능한 분무 수용액, 분말, 현탁액, 또는 고분율의 수성, 유성 또는 기타 현탁액, 또는 분산액, 에멀젼, 오일 분산액, 페이스트, 가루, 살포용 물질 또는 과립의 형태로, 분무, 분사, 더스팅 (dusting), 살포 또는 살수에 의해서 시용될 수 있다. 시용 형태는 목적하는 용도에 따라 다르다; 각각의 경우, 그들은 가능한 본 발명에 따른 활성 화합물이 미세하게 분산되어야 한다. Compounds I and herbicidal compositions containing them are, for example, ready-to-use spray aqueous solutions, powders, suspensions, or high fractions of aqueous, oily or other suspensions, or dispersions, emulsions, oil dispersions, pastes, powders, spraying materials or In the form of granules, it can be applied by spraying, spraying, dusting, spraying or spraying. The type of application depends on the intended use; In each case, they should be as finely dispersed as possible the active compound according to the invention.
적합한 불활성 첨가제로는 주로 케로센 또는 디젤 오일과 같은 중비점 내지 고비점의 무기 오일 분획, 또한 석탄 타르 오일 및 식물 또는 동물 유래 오일, 파라핀유, 테트라히드로나프탈렌, 알킬화된 나프탈렌 또는 그의 유도체, 알킬화된 벤젠 및 그의 유도체와 같은 지방족, 시클릭 및 방향족 탄화수소, 메탄올, 에탄올, 프로판올, 부탄올, 시클로헥사놀, 시클로헥사논, N-메틸피롤리돈과 같은 아민, 및 물과 같은 강한 극성 용매가 있다.Suitable inert additives are mainly middle to high boiling inorganic oil fractions, such as kerosene or diesel oils, as well as coal tar oils and vegetable or animal derived oils, paraffin oils, tetrahydronaphthalenes, alkylated naphthalenes or derivatives thereof, alkylated Aliphatic, cyclic and aromatic hydrocarbons such as benzene and derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, amines such as N-methylpyrrolidone, and strong polar solvents such as water.
수성 용도 형태는 에멀젼 농축물, 분산액, 페이스트, 습윤성 분말 또는 물-분산성 과립으로부터 물을 가함으로써 제조될 수 있다. 에멀젼, 페이스트 또는 오일 분산액을 제조하기 위해서, 오일 또는 용매 중에 용해된 것과 같이, 습윤제, 점착제, 분산제 또는 유화제를 사용하여 기질을 물 중에 균질화시킬 수 있다. 그러나, 활성 성분, 습윤제, 점착제, 분산제 또는 유화제 및 가능하다면, 용매 또는 오일을 함유하는 농축물을 제조할 수 있으며, 그러한 농축물은 물로 희석하는 것이 적합하다.Aqueous use forms can be prepared by adding water from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules. To prepare emulsions, pastes or oil dispersions, wetting agents, tackifiers, dispersants or emulsifiers can be used to homogenize the water, as dissolved in oils or solvents. However, concentrates can be prepared containing the active ingredient, wetting agent, tackifier, dispersant or emulsifier and, if possible, a solvent or oil, which concentrate is suitable for dilution with water.
적합한 계면활성제 (보조제)로는 알칼리 금속염 및 알칼리성 토금속염, 예를 들어, 리그노술폰산, 페놀술폰산, 나프탈렌술폰산 및 디부틸나프탈렌술폰산과 같은 방향족 술폰산의 암모늄염 및 지방산의 암모늄염, 알킬술포네이트 및 알킬아릴술페이트, 알킬술포네이트, 라우릴 에테르 술페이트 및 지방 알코올 술페이트, 및 황산화된 헥사-, 헵타- 및 옥타데카놀의 염, 및 지방 알코올 글리콜 에테르의 염, 황산화된 나프탈렌 및 그의 유도체와 포름알데히드와의 축합물, 나프탈렌 또는 나프탈렌술폰산과 페놀 및 포름알데히드와의 축합물, 폴리옥시에틸렌 옥틸페닐 에테르, 에톡실화된 이소옥틸-, 옥틸- 또는 노닐페놀, 알킬페닐 폴리글리콜 에테르, 트리부틸페닐 폴리글리콜 에테르, 알킬아릴 폴리에테르 알코올, 이소트리데실 알코올, 지방 알코올/에틸렌 옥시드 축합물, 에톡실화된 피마자유, 폴리옥시에틸렌 알킬 에테르 또는 폴리옥시프로필렌 알킬 에테르, 라우릴 알코올 폴리글리콜 에테르 아세테이트, 소르비톨 에스테르, 리그닌술파이트 폐액 또는 메틸셀룰로스가 있다. Suitable surfactants (adjuvant) include alkali metal salts and alkaline earth metal salts, for example ammonium salts of aromatic sulfonic acids such as lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid and ammonium salts of fatty acids, alkylsulfonates and alkylarylsulfates Pate, alkylsulfonate, lauryl ether sulfate and fatty alcohol sulfate, and salts of sulfated hexa-, hepta- and octadecanol, and salts of fatty alcohol glycol ether, sulfated naphthalene and derivatives thereof Condensates with aldehydes, condensates of naphthalene or naphthalenesulfonic acids with phenols and formaldehyde, polyoxyethylene octylphenyl ethers, ethoxylated isooctyl-, octyl- or nonylphenols, alkylphenyl polyglycol ethers, tributylphenyl poly Glycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol / ethyl There are oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin, sulfite waste liquid, or methylcellulose.
분말, 살포제 및 가루 조성물은 활성 물질들을 고체 담체와 함께 혼합 또는 분쇄함으로써 제조될 수 있다. Powders, dusting agents and powder compositions can be prepared by mixing or grinding the active materials with a solid carrier.
코팅된 과립, 함침된 과립 및 균질한 과립과 같은 과립들은 활성 성분들을 고체 담체에 결합시킴으로써 제조될 수 있다. 고체 담체로는 무기 토류 예를 들어, 규산, 실리카겔, 규산염, 활석, 카올린, 석회석, 석회, 쵸크, 교회점토, 황토, 점토, 백운석, 규조토, 황산칼슘, 황산마그네슘, 산화마그네슘, 분쇄된 합성 재료, 비료, 예를 들어 황산암모늄, 인산암모늄, 질산암모늄, 우레아 및 식물 유래의 생성물 예를 들어, 곡분, 목피분, 목분 및 견과 껍질분, 셀룰로스 분말 또는 기타 고체 담체가 있다.Granules such as coated granules, impregnated granules and homogeneous granules can be prepared by binding the active ingredients to a solid carrier. Solid carriers include inorganic earths such as silicic acid, silica gel, silicates, talc, kaolin, limestone, lime, chalk, church clay, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, pulverized synthetic materials Fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and products derived from plants such as cereal flour, bark flour, wood flour and nutshell powder, cellulose powder or other solid carriers.
즉시 사용가능한 제제 중 활성 화합물 I의 농도는 넓은 범위 내에서 변화시킬 수 있다. 통상, 제제는 1 종 이상의 활성 화합물을 약 0.001 내지 98 중량%, 바람직하게는 0.01 내지 95 중량%를 함유한다. 활성 화합물은 90 % 내지 100 %, 바람직하게는 95 % 내지 100 %의 순도로 사용된다 (NMR 스펙트럼에 따라서).The concentration of active compound I in ready-to-use formulations can be varied within a wide range. Usually, the formulation contains about 0.001 to 98% by weight, preferably 0.01 to 95% by weight of one or more active compounds. The active compound is used in purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
본 발명에 따른 화합물 I을 예를 들어, 다음과 같이 제조할 수 있다. Compound I according to the invention can be prepared, for example, as follows.
I. 화합물 번호 13.1 20 중량부를 알킬화된 벤젠 80 중량부, 올레산 N- 모노에탄올아미드 1 몰에 대한 에틸렌 옥시드 8 내지 10몰의 부가물 10 중량부, 칼슘 도데실벤젠술포네이트 5 중량부 및 피마자유 1 몰에 대한 에틸렌 옥시드 40 몰의 부가물 5 중량부를 포함하는 혼합물 중에 용해하였다. 용액을 따라 버리고, 이를 물 100,000 중량부 중에서 잘 분산시킴으로써 활성 성분 0.02 중량%를 함유하는 수분산액을 얻었다. I. Compound No. 13.1 20 parts by weight of 80 parts by weight of alkylated benzene, 10 parts by weight of an adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and castor It was dissolved in a mixture comprising 5 parts by weight of an adduct of 40 moles of ethylene oxide to 1 mole of free. The solution was discarded and dispersed well in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02% by weight of the active ingredient.
II. 화합물 번호 13.3 20 중량부를 시클로헥사논 40 중량부, 이소부탄올 30 중량부, 이소옥틸페놀 40 몰의 부가물 20 중량부 및 피마자유 1 몰에 대한 에틸렌 옥시드 40 몰의 부가물 10 중량부를 포함하는 혼합물 중에 용해시켰다. 용액을 물 100,000 중량부 중에 붓고, 그것을 잘 분산되도록 하여 활성 화합물 0.02 중량%를 함유하는 수분산액을 얻었다. II. Compound No. 13.3 20 parts by weight of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an addition of 40 moles of isooctylphenol and 10 parts by weight of an addition of 40 moles of ethylene oxide to 1 mole of castor oil Dissolved in the mixture. The solution was poured into 100,000 parts by weight of water and allowed to disperse well to obtain an aqueous dispersion containing 0.02% by weight of the active compound.
III. 활성 화합물 번호 13.8 20 중량부를 시클로헥사논 25 중량부, 비점 210 내지 280 ℃의 무기 오일 분획 65 중량부 및 피마자유 1 몰에 대한 에틸렌 옥시드 40 몰의 부가물 10 중량부를 포함하는 혼합물 중에 용해시켰다. 용액을 물 100,000 중량부 중에 붓고, 그것을 잘 분산되도록 하여 활성 화합물 0.02 중량%를 함유하는 수분산액을 얻었다. III. 20 parts by weight of active compound number 13.8 were dissolved in a mixture comprising 25 parts by weight of cyclohexanone, 65 parts by weight of an inorganic oil fraction having a boiling point of 210 to 280 ° C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide to 1 mole of castor oil. . The solution was poured into 100,000 parts by weight of water and allowed to disperse well to obtain an aqueous dispersion containing 0.02% by weight of the active compound.
IV. 활성 화합물 번호 13.9 20 중량부를 디이소부틸나프탈렌-α-술폰산의 나트륨염 3 중량부, 술파이트 폐액으로부터 리그노술폰산의 나트륨염 17 중량부 및 분말 실리카겔 60 중량부와 잘 혼합하고, 그 혼합물을 해머 (hammer) 분쇄기로 분쇄하였다. 물 20,000 중량부 중에 혼합물을 잘 분산되도록 하여 활성 화합물 0.1 중량%를 함유하는 분무 혼합물을 얻었다. IV. 20 parts by weight of active compound No. 13.9 are mixed well with 3 parts by weight of sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of sodium salt of lignosulfonic acid and 60 parts by weight of powdered silica gel from the sulfite waste solution, and the mixture is hammered. It was crushed by a hammer grinder. The mixture was well dispersed in 20,000 parts by weight of water to obtain a spray mixture containing 0.1% by weight of active compound.
V. 활성 화합물 번호 13.5 3 중량부를 잘 분세된 카올린 97 중량부와 혼합하였다. 이러한 방법으로 활성 화합물 3 중량%를 함유하는 가루 조성물을 얻었다.V. 3 parts by weight of active compound No. 13.5 were mixed with 97 parts by weight of well-divided kaolin. In this way a powder composition containing 3% by weight of active compound was obtained.
VI. 활성 화합물 번호 13.15 20 중량부를 도데실벤젠술폰산의 칼슘염 2 중량부, 지방 알코올 폴리글리콜 에테르 8 중량부, 페놀/우레아/포름알데히드 축합물의 나트륨염 2 중량부 및 파라핀 무기 오일 68 중량부과 함께 잘 혼합하였다. 안정한 오일 분산액을 얻었다.VI. Active Compound No. 13.15 20 parts by weight mixed well with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of phenol / urea / formaldehyde condensate and 68 parts by weight of paraffin inorganic oil. It was. A stable oil dispersion was obtained.
VII. 활성 화합물 번호 13.16 1 중량부를 시클로헥사논 70 중량부, 에톡실화된 이소옥틸페놀 20 중량부 및 에톡실화된 피마자유 10 중량부를 포함하는 혼합물 중에 용해하였다. 안정한 에멀젼 농축물을 얻었다.VII. 1 part by weight of active compound No. 13.16 was dissolved in a mixture comprising 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate was obtained.
VIII. 활성 화합물 번호 13.17 1 중량부를 시클로헥사논 80 중량부 및 웨트톨(Wettol) (등록상표) EM 31 (에톡실화된 피마자유를 기재로 하는 비이온성 유화제) 20 중량부를 포함하는 혼합물 중에 용해하였다. 안정한 에멀젼 농축물을 얻었다.VIII. 1 part by weight of active compound No. 13.17 was dissolved in a mixture comprising 80 parts by weight of cyclohexanone and 20 parts by weight of Wetol® EM 31 (nonionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate was obtained.
활성 화합물 I 또는 제초제 조성물은 발아전 또는 발아후에 시용될 수 있다. 특정 농작물의 활성 화합물에 대한 내성이 약한 경우, 제초제 조성물이 분무 장치의 도움으로 분무되는 시용 기술이 사용될 수 있으며, 그러한 방식으로 그들은 민감한 농작물의 잎과 접촉한다하더라도 가능한 적게 접촉하며, 반면 활성 화합물은 아래에 자라고 있는 바람직하지 못한 식물의 잎 또는 노출된 토양 표면에 도달한다 (후방 집중식 레이-바이 처리법 (post-directed, lay-by)).The active compound I or herbicide composition may be applied before or after germination. If the resistance to the active compound of a particular crop is weak, application techniques can be used in which the herbicide composition is sprayed with the aid of a spraying device, in which way they contact as little as possible, even if in contact with the leaves of sensitive crops, whereas the active compound Reach undesired leaf or exposed soil surfaces that grow below (post-directed, lay-by).
억제 목적, 년수, 대상 식물 및 성장 단계에 따라서, 활성 화합물의 시용율은 헥타르 당 활성 물질 (a.s.) 0.001 내지 3.0, 바람직하게는 0.01 내지 1.0 kg이다. Depending on the purpose of inhibition, the number of years, the subject plants and the stage of growth, the application rate of the active compound is from 0.001 to 3.0, preferably 0.01 to 1.0 kg of active substance (a.s.) per hectare.
작용 범위를 넓히고 상승 효과를 얻기 위해서, 벤조일 유도체 I은 수많은 기타 대표적인 제초제 또는 성장 조절 활성 화합물군과 혼합하여 함께 시용될 수 있다. 혼합물의 적당한 성분들로는 예를 들어, 1,2,4-티아디아졸, 1,3,4-티아디아졸, 아미드, 아미노인산 및 그의 유도체, 아미노트리아졸, 아닐리드, 아릴옥시/헤테로아릴옥시 알카노산 및 그의 유도체, 벤조산 및 그의 유도체, 벤조티아디아지논, 2-(헤테로아릴/아로일)-1,3-시클로헥산디온, 헤테로아릴 아릴케톤, 벤질이소옥사졸리디논, 메타-CF3-페닐 유도체, 카르바메이트, 퀴놀린카르복실산 및 그의 유도체, 클로로아세트아닐리드, 시클로헥산-1,3-디온 유도체, 디아진, 디클로로프로피온산 및 그의 유도체, 디히드로벤조푸란, 디히드로푸란-3-온, 디니트로아닐린, 디니트로페놀, 디페닐 에테르, 디피리딜, 할로카르복실산 및 그의 유도체, 우레아, 3-페닐우라실, 이미다졸, 이미다졸리논, N-페닐-3,4,5,6-테트라히드로프탈레이미드, 옥사디아졸, 옥시란, 페놀, 아릴옥시- 및 헤테로아릴옥시페녹시프로피온산 에스테르, 페닐아세트산 및 그의 유도체, 2-페닐프로피온산 및 그의 유도체, 피라졸, 페닐피라졸, 피리다진, 피리딘카르복실산 및 그의 유도체, 피리미딜 에테르, 술폰아미드, 술포닐우레아, 트리아진, 트리아지논, 트리아졸리논, 트리아졸카르복스아미드 및 우라실이 있다.In order to broaden the range of action and obtain a synergistic effect, benzoyl derivative I can be applied together in combination with a number of other representative herbicides or groups of growth regulating active compounds. Suitable components of the mixture include, for example, 1,2,4-thiadiazole, 1,3,4-thiadiazole, amides, aminophosphoric acid and derivatives thereof, aminotriazoles, anilides, aryloxy / heteroaryloxy alka No acid and derivatives thereof, benzoic acid and derivatives thereof, benzothiadiazinone, 2- (heteroaryl / aroyl) -1,3-cyclohexanedione, heteroaryl arylketone, benzylisoxazolidinone, meta-CF 3 -phenyl Derivatives, carbamates, quinolinecarboxylic acids and derivatives thereof, chloroacetanilide, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and derivatives thereof, dihydrobenzofuran, dihydrofuran-3-one, Dinitroaniline, dinitrophenol, diphenyl ether, dipyridyl, halocarboxylic acid and derivatives thereof, urea, 3-phenyluracil, imidazole, imidazolinone, N-phenyl-3,4,5,6 Tetrahydrophthalimide, oxadiazole, oxirane, phenol, aryl jade Cy- and heteroaryloxyphenoxypropionic acid esters, phenylacetic acid and derivatives thereof, 2-phenylpropionic acid and derivatives thereof, pyrazole, phenylpyrazole, pyridazine, pyridinecarboxylic acid and derivatives thereof, pyrimidyl ether, sulfonamide, Sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
또한, 화합물 I을 단독으로, 또는 예를 들어, 살충제 또는 식물 병리학적 곰팡이 또는 세균을 억제하는 제제와 같은 식물 보호제가 추가로 혼합된 다른 제초제와 배합하여 시용하는 것이 유용할 수 있다. 또한, 영양분 및 미량 원소 부족분을 없애는데 사용되는 무기염 용액과의 혼화성도 중요하다. 비-식물독성 오일 및 오일 농축물도 가해질 수 있다.It may also be useful to apply Compound I alone or in combination with other herbicides which are further mixed with, for example, plant protection agents such as pesticides or agents that inhibit plant pathological fungi or bacteria. Also important is compatibility with inorganic salt solutions used to eliminate nutrients and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
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| DE19532311A DE19532311A1 (en) | 1995-09-01 | 1995-09-01 | Benzoyl derivatives |
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| JP3245421B2 (en) * | 1992-08-18 | 2002-01-15 | 出光興産株式会社 | Cyclohexanedione derivative |
| US5559127A (en) * | 1992-10-14 | 1996-09-24 | Merck & Co., Inc. | Fibrinogen receptor antagonists |
| WO1994008988A1 (en) * | 1992-10-15 | 1994-04-28 | Idemitsu Kosan Co., Ltd. | Cyclohexanedione derivative |
| DE4427995A1 (en) * | 1994-08-08 | 1996-02-15 | Basf Ag | Saccharin derivatives |
| EP0846112A1 (en) * | 1995-08-25 | 1998-06-10 | E.I. Du Pont De Nemours And Company | Bicyclic herbicides |
| JP3052862U (en) | 1998-04-01 | 1998-10-09 | サン．フレックス株式会社 | Plate product coating structure that can enhance tourmaline effect |
-
1995
- 1995-09-01 DE DE19532311A patent/DE19532311A1/en not_active Withdrawn
-
1996
- 1996-08-27 TW TW085110391A patent/TW334430B/en not_active IP Right Cessation
- 1996-08-29 EP EP96930128A patent/EP0847394A1/en not_active Withdrawn
- 1996-08-29 CN CN96196604A patent/CN1100052C/en not_active Expired - Fee Related
- 1996-08-29 KR KR10-1998-0701569A patent/KR100446200B1/en not_active IP Right Cessation
- 1996-08-29 CA CA002227934A patent/CA2227934A1/en not_active Abandoned
- 1996-08-29 AU AU69297/96A patent/AU717015B2/en not_active Ceased
- 1996-08-29 SK SK243-98A patent/SK24398A3/en unknown
- 1996-08-29 MX MX9801292A patent/MX9801292A/en unknown
- 1996-08-29 GE GEAP19964208A patent/GEP20012443B/en unknown
- 1996-08-29 EA EA199800233A patent/EA001202B1/en not_active IP Right Cessation
- 1996-08-29 CZ CZ98601A patent/CZ60198A3/en unknown
- 1996-08-29 JP JP9510836A patent/JP3027196B2/en not_active Expired - Fee Related
- 1996-08-29 ZA ZA9607313A patent/ZA967313B/en unknown
- 1996-08-29 HU HU9802430A patent/HUP9802430A3/en unknown
- 1996-08-29 US US09/029,680 patent/US6054414A/en not_active Expired - Fee Related
- 1996-08-29 WO PCT/EP1996/003800 patent/WO1997009324A1/en active IP Right Grant
- 1996-08-29 BR BR9610208A patent/BR9610208A/en unknown
- 1996-08-29 NZ NZ316942A patent/NZ316942A/en unknown
- 1996-08-29 PL PL96325204A patent/PL325204A1/en unknown
- 1996-08-29 IL IL12316596A patent/IL123165A/en not_active IP Right Cessation
- 1996-08-30 AR ARP960104187A patent/AR003688A1/en not_active Application Discontinuation
-
1998
- 1998-03-05 BG BG102297A patent/BG102297A/en unknown
-
1999
- 1999-03-23 JP JP11120316A patent/JP2000026458A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EA001202B1 (en) | 2000-12-25 |
| TW334430B (en) | 1998-06-21 |
| AR003688A1 (en) | 1998-09-09 |
| HUP9802430A3 (en) | 2002-01-28 |
| CA2227934A1 (en) | 1997-03-13 |
| KR19990044329A (en) | 1999-06-25 |
| GEP20012443B (en) | 2001-05-25 |
| SK24398A3 (en) | 1999-01-11 |
| BG102297A (en) | 1998-12-30 |
| MX9801292A (en) | 1998-05-31 |
| EA199800233A1 (en) | 1998-10-29 |
| ZA967313B (en) | 1998-03-02 |
| HUP9802430A2 (en) | 1999-02-01 |
| IL123165A0 (en) | 1998-09-24 |
| CN1194641A (en) | 1998-09-30 |
| IL123165A (en) | 2001-08-08 |
| PL325204A1 (en) | 1998-07-06 |
| JP2000026458A (en) | 2000-01-25 |
| BR9610208A (en) | 1999-02-02 |
| EP0847394A1 (en) | 1998-06-17 |
| JP3027196B2 (en) | 2000-03-27 |
| CN1100052C (en) | 2003-01-29 |
| US6054414A (en) | 2000-04-25 |
| DE19532311A1 (en) | 1997-03-06 |
| WO1997009324A1 (en) | 1997-03-13 |
| AU6929796A (en) | 1997-03-27 |
| NZ316942A (en) | 2000-01-28 |
| AU717015B2 (en) | 2000-03-16 |
| CZ60198A3 (en) | 1998-08-12 |
| JPH10510846A (en) | 1998-10-20 |
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